TWI467068B - Polyurethane elastic yarn and method for production thereof - Google Patents
Polyurethane elastic yarn and method for production thereof Download PDFInfo
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- TWI467068B TWI467068B TW97122792A TW97122792A TWI467068B TW I467068 B TWI467068 B TW I467068B TW 97122792 A TW97122792 A TW 97122792A TW 97122792 A TW97122792 A TW 97122792A TW I467068 B TWI467068 B TW I467068B
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/70—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/285—Nitrogen containing compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
- C08K5/24—Derivatives of hydrazine
- C08K5/26—Semicarbazides
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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Description
本發明係關於一種具有在染色時之高耐熱性(特別是有不飽和脂肪酸或重金屬附著時之高耐熱性)、高彈性回復性及高強伸度等之聚胺基甲酸酯彈性紗及其製造方法。The present invention relates to a polyurethane elastic yarn having high heat resistance at the time of dyeing (especially, high heat resistance when unsaturated fatty acid or heavy metal is attached), high elastic recovery property, high tensile strength, and the like Production method.
彈性纖維係由於其優越的伸縮特性而廣泛地使用於襪子、內衣、運動服等之伸縮性(stretchable)衣料用途或產業資材用途。The elastic fiber is widely used in stretchable clothing applications or industrial materials for socks, underwear, sportswear, and the like because of its superior stretch characteristics.
對於用作為此等彈性纖維所被廣泛使用之聚胺基甲酸酯彈性紗,則要求高強伸度、高彈性回復性(resilience)、高耐熱性、熱定型性(thermosetting property)。其中,高耐熱性係在以與聚酯紗組合的混合布帛之形態使用之用途上受到迫切期望,特別是在染色加工時的耐熱性是非常重要。For the polyurethane elastic yarn which is widely used as such an elastic fiber, high tensile strength, high elastic resilience, high heat resistance, and thermosetting property are required. Among them, high heat resistance is expected to be used in the form of a mixed fabric combined with a polyester yarn, and in particular, heat resistance at the time of dyeing processing is very important.
亦即,在以與聚酯紗之混用來使用之情形、或在使其顯色中間色的情況,則在染色加工時之染色溫度本身有升高之傾向。加上欲獲得良好的伸縮性、尺寸穩定性、表面品質而在染色前以高溫實施乾熱處理之情形也增加。因此,彈性紗則必須為高耐熱性。That is, in the case of being used in combination with a polyester yarn or in the case of rendering an intermediate color, the dyeing temperature itself tends to increase during the dyeing process. In addition, in order to obtain good stretchability, dimensional stability, and surface quality, the dry heat treatment is performed at a high temperature before dyeing. Therefore, the elastic yarn must have high heat resistance.
此外,在彈性紗則有在其製程中所賦予之原紗油劑(yarn finish oil)附著。並且,在混合彈性布帛中,油劑從聚酯紗等之混用紗轉移至彈性紗,使得混用紗之附著油劑附著於彈性紗是必然之事。並且,又有在編織製程中所附 著於編織機械的機械油將會轉移附著在彈性紗上。然而,聚酯紗或耐綸紗中之原紗油劑,一般係使用不飽和脂肪酸。在另一方面,對於用於與該聚酯紗或耐綸紗等混用而構成混合彈性布帛的彈性紗,則會賦予含有不飽和脂肪酸之熱脆化促進物質的油劑。並且,該油劑,雖然為微量,但是也有源於機械的金屬成份等也混入於其中。當在附著於彈性紗的油劑中存在著不飽和脂肪酸之熱脆化促進物質或微量金屬成份時,則由於其相互作用而會促進聚胺基甲酸酯彈性紗之惡化,引起斷紗或局部性的強度降低。並且,視情形而定,也有可能造成布帛的微細穿孔之情況而引起超出預料之非常大的問題。In addition, the elastic yarn is attached to the yarn finish oil imparted in the course of its manufacture. Further, in the hybrid elastic fabric, the oil agent is transferred from the mixed yarn of the polyester yarn or the like to the elastic yarn, so that the adhesion of the lubricating oil to the elastic yarn is inevitable. And, it is attached in the weaving process. The mechanical oil on the weaving machine will transfer and adhere to the elastic yarn. However, the original yarn oil agent in the polyester yarn or the nylon yarn generally uses an unsaturated fatty acid. On the other hand, an elastic yarn containing a thermal embrittlement promoting substance of an unsaturated fatty acid is applied to an elastic yarn which is used in combination with the polyester yarn or the nylon yarn to form a mixed elastic fabric. Further, although the oil agent is in a small amount, it is also incorporated into a mechanical metal component or the like. When a hot embrittlement promoting substance or a trace amount of a metal component of an unsaturated fatty acid is present in an oil agent attached to an elastic yarn, the deterioration of the polyurethane elastic yarn is promoted due to the interaction thereof, causing yarn breakage or Local strength is reduced. Further, depending on the situation, there is a possibility that the fine perforation of the fabric may cause a problem that is unexpectedly large.
因此,強烈地要求即使為在與油劑同時有不飽和脂肪酸或金屬成份附著於彈性紗之狀態下,也必須具有優越的耐熱性。此外,雖然與高耐熱性係相反,但是也要求能在一如既往之溫度下,儘量能在比先前更低溫下進行熱定型。Therefore, it is strongly required to have superior heat resistance even in the state where an unsaturated fatty acid or a metal component is attached to the elastic yarn at the same time as the oil agent. Further, although it is contrary to the high heat resistance, it is required to be heat-set as much as possible at a lower temperature than before, as it is in the past.
然而,為提高抗光脆化性而含有苯并三唑系紫外線吸收劑之聚胺基甲酸酯彈性紗,卻有以含銅的水加以處理時,則有容易泛黃之問題。為了防止該泛黃,已有提案一種使金屬惰性化劑包含在彈性紗中,以使錯合物不至於產生於苯并三唑系紫外線吸收劑與銅之間之技術(參閱發明專利文獻1)。然而,該技術係為提高抗光脆化性而在含有必要量的苯并三唑系紫外線吸收劑之聚胺基甲酸酯彈性紗更進一步地含有金屬惰性劑,以防止苯并三唑系紫外線吸 收劑與銅所引起之泛黃,但是即使添加金屬惰性劑,對於提高聚胺基甲酸酯彈性紗在乾熱處理時或高溫染色時的耐熱性仍然有困難。例如,在染色前以高溫加以乾熱處理之情形、或製成為與聚酯紗之混合布帛而在高溫染色的情況,則其耐熱性依然為無法令人滿意之水準,且也有使用受限之情況。However, when the polyurethane elastic yarn containing a benzotriazole-based ultraviolet absorber for improving light embrittlement resistance is treated with copper-containing water, there is a problem that yellowing is likely to occur. In order to prevent the yellowing, there has been proposed a technique in which a metal inerting agent is contained in an elastic yarn so that the complex compound is not generated between the benzotriazole-based ultraviolet absorber and copper (see Patent Document 1). ). However, this technique further contains a metal inert agent to prevent the photo-brittleness and further contains a metal inert agent in a polyurethane yarn containing a necessary amount of a benzotriazole-based ultraviolet absorber to prevent a benzotriazole system. Ultraviolet absorption The yellowing caused by the charging agent and copper, but even if a metal inert agent is added, it is difficult to improve the heat resistance of the polyurethane elastic yarn during dry heat treatment or high temperature dyeing. For example, in the case of dry heat treatment at a high temperature before dyeing, or in the case of dyeing at a high temperature with a mixed fabric of polyester yarn, the heat resistance is still unsatisfactory, and there are restrictions on use. .
並且,已有提案一種有關為保護由於大氣煙霧及光引起之褪色而使其含有必要量的三氮(triazine)吸光劑與N,N-二烷基半卡肼基(N,N-dialkyl semicarbazide group)之聚胺基甲酸酯彈性紗的技術(參閱發明專利文獻2)。然而,該技術係一種對於為減少大氣煙霧及光引起之褪色而含有必要量的吸光劑之聚胺基甲酸酯彈性紗,更進一步地導入半卡肼基,以防止褪色者,因此,過度添加吸光劑之措施,則會有阻礙在聚胺基甲酸酯彈性紗之乾熱處理時或高溫染色時的耐熱性之傾向。因此,在染色前以高溫加以乾熱處理之情形、或製成為與聚酯紗之混合布帛而在高溫染色之情形等,則其耐熱性係依然為無法令人滿意之水準,且也有使用受限之情況。Moreover, there has been proposed a kind of trinitrogen to protect the fading due to atmospheric smoke and light. (Triazine) A technique of a light absorbing agent and a urethane elastic yarn of an N,N-dialkyl semicarbazide group (see Patent Document 2). However, this technique is a kind of polyurethane elastic yarn containing a necessary amount of light absorbing agent for reducing the fading caused by atmospheric smoke and light, and further introducing a semi-carboxy group to prevent fading, and therefore, excessive The measure of adding a light absorbing agent tends to hinder heat resistance during dry heat treatment of the polyurethane elastic yarn or high temperature dyeing. Therefore, the heat resistance is still unsatisfactory and the use is limited in the case of dry heat treatment at a high temperature before dyeing or in the case of dyeing at a high temperature with a mixed fabric of polyester yarn. The situation.
(發明專利文獻1)日本發明專利特開第2000-169700號公報(發明專利文獻2)發明專利第3028237號公報(Patent Document 1) Japanese Patent Laid-Open Publication No. 2000-169700 (Invention Patent Document 2) Invention Patent No. 3028237
本發明係為解決如上所述之先前技術之問題,而提供 一種即使在高溫染色時有不飽和脂肪酸或重金屬附著於紗也能顯現優越的耐熱性,而且具有高彈性回復性及高強伸度之聚胺基甲酸酯彈性紗,及其製造方法為其目的。The present invention is to solve the problems of the prior art as described above, and to provide A polyurethane elastic yarn which exhibits excellent heat resistance even when an unsaturated fatty acid or a heavy metal adheres to a yarn even at a high temperature dyeing, and which has high elastic recovery property and high elongation, and a method for producing the same.
為達成如前所述之目的,本發明之聚胺基甲酸酯彈性紗係採用以下之措施。For the purpose as described above, the polyurethane elastic yarn of the present invention employs the following measures.
亦即,其特徵為其係由主構成成份為高分子二醇及二異氰酸酯之聚胺基甲酸酯所構成之彈性紗,含有(a)位阻型酚系化合物、(b)N,N-二烷基半卡肼化合物、且(c)含氮芳香族化合物之含量為0.01重量%以上、0.30重量%以下。That is, it is characterized in that it is an elastic yarn composed of a polymer diol having a main constituent component of a polymer diol and a diisocyanate, and contains (a) a sterically hindered phenol compound, (b) N, N. The content of the dialkylcarbazone compound and the (c) nitrogen-containing aromatic compound is 0.01% by weight or more and 0.30% by weight or less.
此外,本發明之聚胺基甲酸酯彈性紗之製造方法,其特徵為在主構成成份為高分子二醇及二異氰酸酯之聚胺基甲酸酯之溶液,添加(a)位阻型酚系化合物、(b)N,N-二烷基半卡肼化合物、及(c)含氮芳香族化合物,製成相對於聚胺基甲酸酯係含有(c)含氮芳香族化合物之比率為0.01重量%以上、0.30重量%以下之聚胺基甲酸酯紡絲溶液後實施紡絲(spinning)。Further, the method for producing a polyurethane elastic yarn of the present invention is characterized in that (a) a hindered phenol is added to a solution in which a main component is a polymer diol and a polyurethane of a diisocyanate. a compound, (b) an N,N-dialkylhalocyanine compound, and (c) a nitrogen-containing aromatic compound, and a ratio of (b) a nitrogen-containing aromatic compound to a polyurethane-based compound Spinning is carried out after a polyurethane spinning solution of 0.01% by weight or more and 0.30% by weight or less.
根據本發明之聚胺基甲酸酯彈性紗,由於其係在高溫染色時即使有不飽和脂肪酸或重金屬附著於紗,也可顯現優越的耐熱性(特別是耐熱老化性),並且,具有高彈性回復性及高強伸度等者,藉由使用該彈性紗所製造之衣服等,則將成為具有優越的脫穿性、適穿性、穿用感、染色 顯色性、耐變色性、外觀品質等等者。The polyurethane elastic yarn according to the present invention exhibits superior heat resistance (especially heat aging resistance) even when unsaturated fatty acid or heavy metal adheres to the yarn at high temperature dyeing, and has high The elastic resilience, high tensile strength, etc., by using the clothes made of the elastic yarn, etc., will have excellent peelability, wearability, wearing feeling, and dyeing. Color rendering, discoloration resistance, appearance quality, etc.
以下,就本發明更詳細加以說明。Hereinafter, the present invention will be described in more detail.
首先,就用於構成本發明之聚胺基甲酸酯彈性紗的基質高分子之聚胺基甲酸酯加以說明。First, a polyurethane of a matrix polymer constituting the polyurethane elastic yarn of the present invention will be described.
使用於本發明之聚胺基甲酸酯,只要其為主構成成份為高分子二醇及二異氰酸酯之聚胺基甲酸酯時,則並無特殊的限制而可為任意者。此外,其合成法也並無特殊的限制。The polyurethane to be used in the present invention is not particularly limited as long as it is a polymer diol and a polyisocyanate of a diisocyanate. In addition, there are no special restrictions on the synthesis method.
亦即,例如可為由高分子二醇、二異氰酸酯及低分子量二胺所構成之聚胺基甲酸酯-脲,此外,也可為由高分子二醇、二異氰酸酯及低分子量二醇所構成之聚胺基甲酸酯。此外,也可為使用在分子內具有羥基與胺基之化合物作為鏈段增長劑之聚胺基甲酸酯-脲。此外,也可在不至於抑制本發明之功效範圍內併用三官能性以上之多官能性之二醇或異氰酸酯等。That is, for example, it may be a polyurethane-urea composed of a polymer diol, a diisocyanate, and a low molecular weight diamine, or may be a polymer diol, a diisocyanate, or a low molecular weight diol. A polyurethane formed. Further, a polyurethane-urea which uses a compound having a hydroxyl group and an amine group in a molecule as a segment growth agent may also be used. Further, a polyfunctional diol or an isocyanate or the like having a trifunctional or higher functionality may be used in combination without inhibiting the efficacy of the present invention.
茲就用於構成在本發明使用之聚胺基甲酸酯之代表性結構單元說明如下。Representative structural units for constituting the polyurethane used in the present invention are explained below.
用於構成聚胺基甲酸酯的結構單元之高分子二醇較佳為聚醚系二醇、聚酯系二醇、聚碳酸酯二醇等。並且,從特別是對於彈性紗賦予柔軟性、伸度的觀點來考慮,則較佳為使用聚醚系二醇。The polymer diol used for the structural unit constituting the polyurethane is preferably a polyether diol, a polyester diol, a polycarbonate diol or the like. Further, from the viewpoint of imparting flexibility and elongation to the elastic yarn in particular, it is preferred to use a polyether diol.
聚醚系二醇較佳為包含具有以下列通式(I)所代表之
單元之共聚合二醇化合物:
該「聚醚系二醇化合物」,具體言之,其係包括:聚乙二醇、改質聚乙二醇、聚丙二醇、聚三亞甲基醚二醇、聚四亞甲基醚二醇(在下文中,簡稱為「PTMG」)、四氫呋喃(在下文中,簡稱為「THF」)及3-甲基-THF之共聚合物的改質PTMG、THF及2,3-二甲基-THF之共聚合物的改質PTMG、THF及新戊二醇之共聚合物的改質PTMG、THF與環氧乙烷和/或環氧丙烷係不規則配列的無規共聚合物等。可使用此等聚醚系二醇類之一種、也可混合兩種以上使用或加以共聚合使用。其中,較佳為PTMG或改質PTMG。The "polyether diol compound" specifically includes polyethylene glycol, modified polyethylene glycol, polypropylene glycol, polytrimethylene ether glycol, and polytetramethylene ether glycol ( In the following, abbreviated as "PTMG", tetrahydrofuran (hereinafter, abbreviated as "THF") and 3-methyl-THF copolymer modified PTMG, THF and 2,3-dimethyl-THF The polymer is modified with PTMG, a modified PTFE of THF and neopentyl glycol, a random copolymer of THF and ethylene oxide and/or propylene oxide, and the like. One type of these polyether diols may be used, or two or more types may be used in combination or copolymerized. Among them, PTMG or modified PTMG is preferred.
此外,從提高聚胺基甲酸酯紗之耐摩耗性或耐光性的觀點來考慮,則較佳為使用己二酸丁二醇酯、聚己內酯二醇、將3-甲基-1,5-戊二醇與聚伸丙基多元醇之混合物與己二酸等進行縮聚合反應所獲得之具有側鏈的聚酯二醇等之聚酯系二醇、或含有從由3,8-二甲基癸二酸和/或3,7-二甲基癸二酸所構成之二羧酸成份與二醇成份所衍生之二羧酸酯單元之聚碳酸酯二醇等。Further, from the viewpoint of improving the abrasion resistance and light resistance of the polyurethane yarn, it is preferred to use butylene adipate, polycaprolactone diol, and 3-methyl-1. a polyester diol having a side chain of a polyester diol obtained by a polycondensation reaction of a mixture of 5-pentanediol and a poly(extension propylene polyol) with adipic acid or the like, or containing 3,8 a polycarbonate diol comprising a dicarboxylic acid component composed of dimethyl sebacic acid and/or 3,7-dimethyl sebacic acid and a dicarboxylic acid ester unit derived from a diol component.
此外,此等高分子二醇可以單獨使用、也可混合兩種以上或加以共聚合使用。Further, these polymer diols may be used singly or in combination of two or more kinds or copolymerized.
此等高分子二醇之分子量,為使其製成為彈性紗時之伸度、強度、耐熱性等能達到吾所欲之水準,則較佳為以數量平均分子量計為1,000至8,000,更佳為1,800至6,000。藉由使用分子量在該範圍之高分子二醇,則可獲得具有優越的伸度、強度、彈性回復力、耐熱性之彈性紗。The molecular weight of these high molecular weight diols is preferably from 1,000 to 8,000, preferably from 1,000 to 8,000, in terms of number average molecular weight, in order to achieve the desired level of elongation, strength, heat resistance, etc. when the elastic yarn is made into an elastic yarn. It is 1,800 to 6,000. By using a polymer diol having a molecular weight in this range, an elastic yarn having excellent elongation, strength, elastic restoring power, and heat resistance can be obtained.
其次,用於構成聚胺基甲酸酯的結構單元之二異氰酸酯,特別是從合成耐熱性或強度為高之聚胺基甲酸酯的觀點來考慮,則較佳為使用二苯甲烷二異氰酸酯(在下文中,簡稱為「MDI」)、伸甲苯基二異氰酸酯、苯1,4-二異氰酸酯、苯二甲基二異氰酸酯、2,6-萘二異氰酸酯等之「芳香族二異氰酸酯」。並且,「脂環族二異氰酸酯」較佳為例如,亞甲基-雙(4-環己基異氰酸酯)(在下文中,簡稱為「PICM」。)、異佛酮二異氰酸酯、甲基環己烷-2,4-二異氰酸酯、甲基環己烷-2,6-二異氰酸酯、環己烷-1,4-二異氰酸酯、六氫苯二甲基二異氰酸酯、六氫伸甲苯基二異氰酸酯、八氫-1,5-萘二異氰酸酯等。「脂肪族二異氰酸酯」係可有效使用於特別是欲抑制聚胺基甲酸酯彈性紗之泛黃時。並且,此等之二異氰酸酯係可單獨使用、或併用兩種以上。Next, the diisocyanate used to constitute the structural unit of the polyurethane, particularly from the viewpoint of synthesizing a polyurethane having high heat resistance or strength, is preferably a diphenylmethane diisocyanate. (hereinafter, simply referred to as "MDI"), "aromatic diisocyanate" such as tolyl diisocyanate, benzene 1,4-diisocyanate, benzodimethyl diisocyanate or 2,6-naphthalene diisocyanate. Further, the "alicyclic diisocyanate" is preferably, for example, methylene-bis(4-cyclohexyl isocyanate) (hereinafter, abbreviated as "PICM"), isophorone diisocyanate, methylcyclohexane- 2,4-diisocyanate, methylcyclohexane-2,6-diisocyanate, cyclohexane-1,4-diisocyanate, hexahydrobenzodimethylisocyanate, hexahydro-tolyl diisocyanate, octahydrogen -1,5-naphthalene diisocyanate or the like. The "aliphatic diisocyanate" is effective for particularly suppressing the yellowing of the polyurethane elastic yarn. Further, these diisocyanates may be used singly or in combination of two or more.
其次,用於構成聚胺基甲酸酯的結構單元之鏈段增長劑較佳為使用低分子量二胺及低分子量二醇之中至少一種以上。此外,也可為例如乙醇胺之在分子中具有羥基與胺 基者。Next, it is preferred to use at least one of a low molecular weight diamine and a low molecular weight diol for the segment growth agent constituting the structural unit of the polyurethane. In addition, it may also be, for example, ethanolamine having a hydroxyl group and an amine in the molecule. Base.
低分子量二胺及低分子量二醇之分子量較佳為30至300,且從欲獲得高熔點聚胺基甲酸酯的觀點來考慮,則更佳為40至200。The molecular weight of the low molecular weight diamine and the low molecular weight diol is preferably from 30 to 300, and more preferably from 40 to 200 from the viewpoint of obtaining a high melting point polyurethane.
較佳的「低分子量二胺」係包括:例如,肼(聯胺;hydrazine)、伸乙二胺、1,2-丙二胺、1,3-丙二胺、六亞甲基二胺、對-伸苯基二胺、對-苯二甲基二胺、間-苯二甲基二胺、對,對’-亞甲基二苯胺、1,3-環己基二胺、六氫甲基伸苯基二胺、2-甲基五亞甲基二胺、雙(4-胺基苯基)氧化膦等。較佳為從此等之中使用一種或兩種以上,且特佳為伸乙二胺。藉由使用伸乙二胺,則可製得具有優越的伸度及彈性回復性、以及耐熱性之紗。也可在不至於喪失本發明之吾所欲之功效的程度,對於此等之鏈段增長劑加入例如二伸乙三胺等之可形成交聯結構之三胺化合物。Preferred "low molecular weight diamines" include, for example, hydrazine, hydrazine, ethylenediamine, 1,2-propylenediamine, 1,3-propanediamine, hexamethylenediamine, P-phenylenediamine, p-xylylenediamine, m-phenylenediamine, p-, p-methylenediphenylamine, 1,3-cyclohexyldiamine, hexahydromethyl Phenyldiamine, 2-methylpentamethylenediamine, bis(4-aminophenyl)phosphine oxide, and the like. It is preferred to use one or two or more kinds from among them, and particularly preferably ethylenediamine. By using ethylenediamine, a yarn having superior elongation, elastic recovery, and heat resistance can be obtained. To the extent that the effect of the present invention is not lost, a triamine compound which forms a crosslinked structure such as diethylenetriamine or the like may be added to such a chain extender.
此外,「低分子量二醇」之代表性者係包括:乙二醇、1,3-丙二醇、1,4-丁二醇、雙羥基乙氧基苯、對苯二甲酸雙羥基乙二醇酯、1-甲基-1,2-乙烷二醇等。較佳為從此等之中使用一種或兩種以上。特佳的是乙二醇、1,3-丙二醇、1,4-丁二醇。若使用此等時,以二醇伸長之聚胺基甲酸酯而言,則可製得耐熱性高、且強度高之紗。In addition, representative of "low molecular weight diol" includes: ethylene glycol, 1,3-propanediol, 1,4-butanediol, bishydroxyethoxybenzene, bishydroxyethylene terephthalate , 1-methyl-1,2-ethanediol, and the like. It is preferred to use one or two or more kinds from these. Particularly preferred are ethylene glycol, 1,3-propanediol, and 1,4-butanediol. When such a product is used, a diol-extended polyurethane can produce a yarn having high heat resistance and high strength.
此外,用於構成本發明之聚胺基甲酸酯彈性紗之聚胺基甲酸酯之分子量,從欲獲得耐久性或高強度之纖維的觀點而言,則較佳為數量平均分子量為在40,000以上、150,000以下之範圍。此外,分子量係藉由GPC所測定, 且以聚苯乙烯換算所計算得之值。Further, the molecular weight of the polyurethane used to constitute the polyurethane elastic yarn of the present invention is preferably a number average molecular weight from the viewpoint of obtaining durability or high strength fibers. 40,000 or more and 150,000 or less. In addition, the molecular weight is determined by GPC. And the value calculated in terms of polystyrene.
並且,用於構成本發明之彈性紗之聚胺基甲酸酯,特佳的是從欲獲得一種並無包括製程通過性在內之實務應用上的問題、且具有優越的高耐熱性者的觀點來考慮,則為由高分子二醇與二異氰酸酯所構成,且高溫側之熔點為在200℃以上、300℃以下之範圍者。在此所謂的「高溫側之熔點」係相當於藉由DSC(示差掃描熱量測定計)測定時,聚胺基甲酸酯或聚胺基甲酸酯-脲之所謂的「硬質鏈段結晶之熔點」。Further, the polyurethane used to constitute the elastic yarn of the present invention is particularly preferable from the viewpoint of obtaining a problem of practical application including no process passability and having superior high heat resistance. In view of the above, the polymer diol and the diisocyanate are used, and the melting point on the high temperature side is in the range of 200 ° C or more and 300 ° C or less. Here, the "melting point on the high temperature side" corresponds to the so-called "hard segmental crystallization" of polyurethane or polyurethane-urea when measured by DSC (differential scanning calorimeter). Melting point".
亦即,藉由使用分子量為1,000以上、6,000以下範圍之PTMG作為高分子二醇,MDI作為二異氰酸酯,選自由乙二醇、1,3-丙二醇、1,4-丁二醇、伸乙二胺、1,2-丙二胺、1,3-丙二胺所組成的族群中之至少一種作為鏈段增長劑所聚合而成之聚胺基甲酸酯,且高溫側之熔點為在200℃以上、300℃以下之範圍之聚胺基甲酸酯所製造之彈性紗,由於其係特別是伸度將提高、並無包括製程通過性之實務應用上的問題、且具有優越的耐熱性,因此為較佳。That is, by using PTMG having a molecular weight of 1,000 or more and 6,000 or less as a polymer diol, MDI is used as a diisocyanate selected from ethylene glycol, 1,3-propanediol, 1,4-butanediol, and ethylene-2. a polyurethane obtained by polymerizing at least one of a group consisting of an amine, 1,2-propylenediamine, and 1,3-propanediamine as a segment growth agent, and having a melting point of 200 at a high temperature side Elastic yarns made of polyurethanes in the range of °C or more and 300 °C or less are particularly excellent in elongation, do not include problems in practical application of process passability, and have excellent heat resistance. Therefore, it is better.
此外,為使聚胺基甲酸酯紗之高溫側的熔點達到200℃以上、300℃以下之方法,較佳為以預先試驗來選擇二異氰酸酯與高分子二醇、鏈段增長劑之比率的最適值之方法。此等聚胺基甲酸酯係適合用作為在本發明使用之聚胺基甲酸酯。Further, in order to achieve a melting point of the high temperature side of the polyurethane yarn of 200 ° C or more and 300 ° C or less, it is preferred to select a ratio of the diisocyanate to the polymer diol and the segment growth agent by a preliminary test. The method of optimal value. These polyurethanes are suitable for use as the polyurethane used in the present invention.
本發明之聚胺基甲酸酯彈性紗係將如上所述之聚胺基甲酸酯用作為基質高分子,並且含有(a)位阻型酚系化合 物、(b)N,N-二烷基半卡肼化合物、及(c)含氮芳香族化合物者,且(c)含氮芳香族化合物之含量為0.01重量%以上、0.30重量%以下。The polyurethane elastic yarn of the present invention uses the above-mentioned polyurethane as a matrix polymer and contains (a) a sterically hindered phenol compound. And (b) a nitrogen-containing aromatic compound, and (c) a nitrogen-containing aromatic compound is contained in an amount of 0.01% by weight or more and 0.30% by weight or less.
(a)位阻型酚系化合物(在下文中,簡稱為「(a)化合物」)、(b)N,N-二烷基半卡肼化合物(在下文中,簡稱為「(b)化合物」)、及(c)含氮芳香族化合物(在下文中,簡稱為「(c)化合物」)係不僅在提高藉由捕捉自由基的抗氧化功效等之一般耐熱老化性、或藉由吸收特定紫外線之一般耐光性上是有效,而且能捕捉不飽和脂肪酸與金屬成份以使其無害化,藉此則可提高對於此等之聚胺基甲酸酯彈性紗之耐劣化性。(a) a sterically hindered phenol-based compound (hereinafter, simply referred to as "(a) compound"), (b) an N,N-dialkylsemicarbazone compound (hereinafter, simply referred to as "(b) compound") And (c) a nitrogen-containing aromatic compound (hereinafter, simply referred to as "(c) compound") is not only improved in general heat aging resistance by capturing the antioxidant effect of a radical, etc., or by absorbing specific ultraviolet rays. It is generally effective in light resistance, and can capture unsaturated fatty acids and metal components to make them harmless, thereby improving the deterioration resistance of the polyurethane elastic yarns.
具體言之,(a)化合物、(b)化合物及(c)化合物係主要以增效金屬捕捉之方式來發生作用,(a)化合物及(b)化合物則係以增效捕捉不飽和脂肪酸之方式來發生作用。因此,藉由併用此等之化合物,即使附著不飽和脂肪酸或重金屬之聚胺基甲酸酯彈性紗在高溫染色之情況下,也能發揮優越的耐熱性,而顯現本發明之吾所欲之功效。並且,若在(c)化合物之含量(相對於紗之比率)為0.01重量%以上、0.30重量%以下的情況,則該功效可藉由與(a)化合物及(b)化合物之增效功效而提高抗氧化功效,充分捕捉在染色時所混入之微量(100 ppm以下)重金屬而使其無害化。在此所謂的(c)化合物之含量(相對於紗之比率)的0.01重量%以上、0.30重量%以下,一般而言,其係相當於芳香環氮原子係在每1公斤紗中以5 至200毫當量(meq/kg)之範圍存在之情形。Specifically, the (a) compound, the (b) compound, and the (c) compound act mainly in the manner of synergistic metal capture, and the (a) compound and the (b) compound synergistically capture unsaturated fatty acids. The way to make a difference. Therefore, by using these compounds in combination, even if the polyurethane elastic yarn to which an unsaturated fatty acid or a heavy metal is attached is dyed at a high temperature, superior heat resistance can be exerted, and the present invention is intended to exhibit the desired heat. efficacy. Further, when the content of the compound (c) (ratio to the yarn) is 0.01% by weight or more and 0.30% by weight or less, the effect can be enhanced by the synergistic effect with the compound (a) and the compound (b). It improves the antioxidant effect and fully captures the trace amount (less than 100 ppm) of heavy metals mixed in the dyeing to make it harmless. Here, the content of the compound (c) (the ratio with respect to the yarn) is 0.01% by weight or more and 0.30% by weight or less, and generally corresponds to an aromatic ring nitrogen atom system of 5 per 1 kg of yarn. The case exists in the range of 200 milliequivalents (meq/kg).
與此相對,由於含有氮原子之芳香環係容易發生熱分解,若(c)化合物之含量為多時(亦即,芳香環氮原子為超過200毫當量之量時),則比與(a)化合物及(b)化合物之增效功效,由於熱分解引起的自由基產生將佔優勢,使得耐熱性降低、或形成醌結構而引起熱變色,因此,不能獲得在染色時的高耐熱性等之功能。此外,雖然也有將(c)化合物用作為耐光劑而使其含有多量之情況,但是其含量若為多至超過0.30重量%之程度時,則無法獲得作為本發明之目的之在染色時之高耐熱性等功效。基於如上所述之各觀點,較佳為(c)化合物之含量為不至於過多之適當量。具體言之,較佳的範圍為0.01至0.25重量%,更佳為0.05至0.20重量%,最佳為0.07至1.80重量%。On the other hand, since the aromatic ring system containing a nitrogen atom is likely to be thermally decomposed, and when the content of the compound (c) is large (that is, when the aromatic ring nitrogen atom is more than 200 milliequivalents), the ratio (a) The synergistic effect of the compound and the compound (b), the radical generation due to thermal decomposition will predominate, the heat resistance is lowered, or the ruthenium structure is formed to cause thermal discoloration, and therefore, high heat resistance at the time of dyeing cannot be obtained. The function. Further, although the compound (c) may be used as a light stabilizer to contain a large amount, if the content is as large as more than 0.30% by weight, the dyeing time is not obtained as the object of the present invention. Heat resistance and other effects. Based on the above viewpoints, it is preferred that the content of the compound (c) is an appropriate amount which is not excessive. Specifically, a preferred range is from 0.01 to 0.25% by weight, more preferably from 0.05 to 0.20% by weight, most preferably from 0.07 to 1.80% by weight.
並且,即使缺少(a)化合物及(b)化合物中之任一者,對於耐不飽和脂肪酸與耐金屬之捕捉功效仍然為無法令人滿意者。此外,此等之含量雖然為獲得本發明之功效而較佳為含有多至某一程度,但是若增加過多時,則容易損及聚胺基甲酸酯彈性紗固有之優良特性,因此,(a)化合物含量較佳為0.1重量%以上、6.0重量%以下,(b)化合物含量則較佳為1.0重量%以上、6.0重量%以下。Further, even if either of the (a) compound and the (b) compound is absent, the capture efficiency against unsaturated fatty acids and metal resistance is still unsatisfactory. Further, although the content of these is preferably contained to a certain extent in order to obtain the effect of the present invention, if the amount is excessively increased, the inherent properties of the polyurethane elastic yarn are easily impaired, and therefore, a) The content of the compound is preferably 0.1% by weight or more and 6.0% by weight or less, and the content of the compound (b) is preferably 1.0% by weight or more and 6.0% by weight or less.
如上所述,在本發明中,則必須在聚胺基甲酸酯彈性紗中,同時含有(a)位阻型酚系化合物、(b)N,N-二烷基半卡肼化合物、及(c)含氮芳香族化合物。As described above, in the present invention, it is necessary to contain (a) a hindered phenol compound, (b) an N,N-dialkylhalocyanine compound, and (c) A nitrogen-containing aromatic compound.
在本發明使用之「(a)化合物」,亦即,「位阻型 酚系化合物」係包括以一般作為抗氧化劑而為眾所知的酚系化合物。例如,3,5-二-三級-丁基-4-羥基-甲苯、正-十八烷基-β-(4’-羥基-3’,5’-二-三級-丁基苯基)丙酸酯、肆〔亞甲基-3-(3’,5’-二-三級-丁基-4’-羥基苯基)丙酸酯〕甲烷、1,3,5-三甲基-2,4,6’-參(3,5-二-三級-丁基-4-羥基苯甲基)苯、鈣(3,5-二-三級-丁基-4-羥基-苯甲基-一乙基-磷酸酯)、三甘醇-雙〔3-(3-三級-丁基-5-甲基-4-羥基苯基)丙酸酯〕、3,9-雙〔1,1-二甲基-2-{β-(3-三級-丁基-4-羥基-5-甲基苯基)丙醯氧基}乙基〕2,4,8,10-四氧螺〔5,5〕十一烷、生育酚(tocopherol)、2,2’-亞乙基雙(4,6-二-三級-丁基苯酚)、N,N’-雙〔3-(3,5-二-三級-丁基-4-羥基苯基)丙醯基〕肼、2,2’-草醯胺雙〔乙基-3-(3,5-二-三級-丁基-4-羥基苯基)丙酸酯〕、1,1,3-參(2-甲基-4-羥基-5-三級-丁基苯基)丁烷、伸乙基-1,2-雙(3,3-雙〔3-三級-丁基-4-羥基苯基〕丁酸酯)、伸乙基-1,2-雙(3-〔3-三級-丁基-4-羥基苯基〕丁酸酯)、1,1-雙(2-甲基-5-三級-丁基-4-羥基苯基)丁烷、1,1,3-參(2-甲基-5-三級-丁基-4-羥基苯基)丁烷、1,3,5-參(3’,5’-二-三級-丁基-4’-羥基苯甲基)-S-三氮-2,4,6(1H,3H,5H)-三酮、1,3,5-參(3’-三級-丁基-4’-羥基-5-甲基苯甲基)-S-三氮-2,4,6(1H,3H,5H)-三酮、1,3,5-參(4-三級-丁基-3-羥基-2,6-二甲基苯甲基)-1,3,5-三氮-2,4,6(1H,3H,5H)-三酮,並且,聚胺基甲酸酯彈性紗用之抗氧化劑也適合使用眾所皆知的高分子量之位阻型酚系化合物。The "(a) compound" used in the present invention, that is, the "hindered phenolic compound" includes a phenolic compound which is generally known as an antioxidant. For example, 3,5-di-tris-butyl-4-hydroxy-toluene, n-octadecyl-β-(4'-hydroxy-3',5'-di-tertiary-butylphenyl Propionate, hydrazine [methylene-3-(3',5'-di-tertiary-butyl-4'-hydroxyphenyl)propionate]methane, 1,3,5-trimethyl -2,4,6'-parade (3,5-di-tris-butyl-4-hydroxybenzyl)benzene, calcium (3,5-di-tertiary-butyl-4-hydroxy-benzene Methyl-ethyl-phosphate), triethylene glycol-bis[3-(3-tris-butyl-5-methyl-4-hydroxyphenyl)propionate], 3,9-double 1,1-dimethyl-2-{β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoxy}ethyl]2,4,8,10-tetra Oxyspiro[5,5]undecane, tocopherol, 2,2'-ethylenebis(4,6-di-tertiary-butylphenol), N,N'-bis[3- (3,5-di-tris-butyl-4-hydroxyphenyl)propanyl]anthracene, 2,2'-oxalylamine bis[ethyl-3-(3,5-di-tris- Butyl-4-hydroxyphenyl)propionate], 1,1,3-glycol(2-methyl-4-hydroxy-5-tertiary-butylphenyl)butane, Ethyl-1,2-bis(3,3-bis[3-tert-butyl-4-hydroxyphenyl]butyrate), ethylidene-1,2-bis(3-[3-three Grade-butyl-4-hydroxyphenyl]butyrate), 1,1-bis(2-methyl-5-tris-butyl-4-hydroxyphenyl)butane, 1,1,3- ((2-methyl-5-tertiary-butyl-4-hydroxyphenyl)butane, 1,3,5-paran (3',5'-di-tertiary-butyl-4'-hydroxyl Benzyl)-S-trinitrogen -2,4,6(1H,3H,5H)-trione, 1,3,5-gin (3'-tertiary-butyl-4'-hydroxy-5-methylbenzyl)-S- Trinitrogen -2,4,6(1H,3H,5H)-trione, 1,3,5-gin (4-tris-butyl-3-hydroxy-2,6-dimethylbenzyl)-1 , 3,5-trinitrogen -2,4,6(1H,3H,5H)-trione, and the antioxidant for the polyurethane elastic yarn is also suitably used for the well-known high molecular weight sterically hindered phenolic compound.
此等高分子量之位阻型酚系化合物之較佳的具體實例係使用二乙烯基苯與甲酚之加成聚合物、二環戊二烯與甲酚之加成聚合物異丁烯加成物、氯甲基苯乙烯與甲酚、乙基苯酚、三級-丁基苯酚等之化合物的聚合物。其中,二乙烯基苯、氯甲基苯乙烯係可為對位-、或間位-。此外,甲酚、乙基苯酚、三級-丁基苯酚係可為鄰位-、間位-、對位-中之任一者。Preferred specific examples of such high molecular weight sterically hindered phenolic compounds are the use of an addition polymer of divinylbenzene and cresol, an addition polymer of dicyclopentadiene and cresol, an isobutylene adduct, A polymer of a compound of chloromethylstyrene and cresol, ethylphenol, tert-butylphenol or the like. Among them, divinylbenzene and chloromethylstyrene may be para- or meta-. Further, cresol, ethylphenol, and tertiary butylphenol may be either ortho-, meta-, or para-.
其中,從將聚胺基甲酸酯紗的原料紡絲液之黏度加以穩定化、抑制紡絲中之揮發減量、獲得良好的可紡絲性的觀點來考慮,則較佳為分子量為300以上之化合物,並且,欲有效地發揮高紡絲速度、在染色時之耐熱性、對於不飽和脂肪酸之耐性、對於重金屬之耐性時,則較佳為使用1,3,5-參(4-三級-丁基-3-羥基-2,6-二甲基苯甲基)-1,3,5-三氮-2,4,6(1H,3H,5H)-三酮、三甘醇-雙〔3-(3-三級-丁基-5-甲基-4-羥基苯基)丙酸酯〕、伸乙基-1,2-雙(3,3-雙〔3-三級-丁基-4-羥基苯基〕丁酸酯)、二乙烯基苯與對-甲酚之加成物、且具有6至12之重覆數之聚合物中任一或併用此等來使用。其中,特佳為1,3,5-參(4-三級-丁基-3-羥基-2,6-二甲基苯甲基)-1,3,5-三氮-2,4,6(1H,3H,5H)-三酮。此外,若(a)化合物及(c)化合物選擇三氮化合物時,則在染色時之耐熱性方面,可獲得特別高的增效功效。其中,特佳的是(a)化合物為1,3,5-參(4-三級-丁基-3-羥基-2,6-二甲基苯甲基)-1,3,5-三氮-2,4,6(1H,3H,5H)-三酮,且(c)化合物為2,4-二( 2’,4’-二甲基苯基)-6-(2”-羥基-4”-烷氧基苯基)-1,3,5-三氮。Among them, from the viewpoint of stabilizing the viscosity of the raw material spinning solution of the polyurethane yarn, suppressing the amount of volatilization in the spinning, and obtaining good spinnability, the molecular weight is preferably 300 or more. For the purpose of effectively exhibiting high spinning speed, heat resistance during dyeing, resistance to unsaturated fatty acids, and resistance to heavy metals, it is preferred to use 1,3,5-para (4-three Grade-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazole -2,4,6(1H,3H,5H)-trione, triethylene glycol-bis[3-(3-tris-butyl-5-methyl-4-hydroxyphenyl)propionate], Ethyl-1,2-bis(3,3-bis[3-tris-butyl-4-hydroxyphenyl]butyrate), an adduct of divinylbenzene and p-cresol, and Any of the polymers having a repeat number of 6 to 12 or used in combination. Among them, particularly preferred is 1,3,5-gin (4-tris-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazole -2,4,6(1H,3H,5H)-trione. In addition, if (a) compound and (c) compound select trinitrogen In the case of a compound, a particularly high synergistic effect can be obtained in terms of heat resistance at the time of dyeing. Among them, it is particularly preferred that the compound (a) is 1,3,5-gin(4-tris-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-three nitrogen -2,4,6(1H,3H,5H)-trione, and the compound (c) is 2,4-bis(2',4'-dimethylphenyl)-6-(2"-hydroxy- 4"-alkoxyphenyl)-1,3,5-triazole .
在本發明使用之「(b)化合物」,除了其為N,N-二烷基半卡肼化合物,且為在分子內具有N,N-二烷基半卡肼之化合物以外,其他並無特殊的限制。例如,可為分子量為約1,000以下之較低分子量之單體型者(在下文中,稱為「單體型N,N-二烷基半卡肼」)。並且,也可為分子量為約1,000以上之較高分子量之寡聚物或高分子,且在末端具有N,N-二烷基半卡肼之寡聚物型或高分子型(在下文中,稱為「在末端具有N,N-二烷基半卡肼之聚合物」)。此外,也較佳的是併用單體型N,N-二烷基半卡肼及在末端具有N,N-二烷基半卡肼之聚合物。The "(b) compound" used in the present invention is other than the compound having an N,N-dialkylcarbazone compound in the molecule and having N,N-dialkylcarbazone in the molecule. Special restrictions. For example, it may be a lower molecular weight haplotype having a molecular weight of about 1,000 or less (hereinafter, referred to as "monomeric N,N-dialkylhalfcaquinone"). Further, it may be an oligomer or a polymer having a relatively high molecular weight of about 1,000 or more, and an oligomer type or a polymer type having an N,N-dialkylcarbazone at the terminal (hereinafter, referred to as It is "a polymer having an N,N-dialkylhalf-anthracene at the end"). Further, it is also preferred to use a monomeric N,N-dialkylhalocarbamate and a polymer having an N,N-dialkylhalfquinone at the terminal.
「單體型N,N-二烷基半卡肼」之較佳的具體實例係包括:例如,1,6-六亞甲基雙(N,N-二甲基半卡肼)、4,4’-(亞甲基二-對-伸苯基)雙(N,N-二甲基半卡肼)、4,4’-(亞甲基二-對-伸苯基)雙(N,N-二乙基半卡肼)、4,4’-(亞甲基二-對-伸苯基)雙(N,N-二-異-丙基半卡肼)、α,α-(對-苯二甲基)雙(N,N-二甲基半卡肼)、1,4-伸環己基雙(N,N-二甲基半卡肼)、雙縮脲-三(六亞甲基-N,N-二甲基半卡肼)等。特佳的是1,6-六亞甲基雙(N,N-二甲基半卡肼)、4,4’-(亞甲基二-對-伸苯基)雙(N,N-二甲基半卡肼)。Preferred specific examples of the "monomeric N,N-dialkylcarbazone" include, for example, 1,6-hexamethylenebis(N,N-dimethylhalocanthene), 4, 4'-(methylenedi-p-phenylene) bis(N,N-dimethylhalocyanine), 4,4'-(methylenedi-p-phenylene) bis(N, N-diethylcarbazone), 4,4'-(methylenebis-p-phenylene)bis(N,N-di-iso-propylhalocyanine), α,α-(pair - Benzyl) bis(N,N-dimethylhalocanthene), 1,4-cyclohexyl bis(N,N-dimethylhalocanthine), biuret-three (hexamethylene) Base-N,N-dimethylsemicarbazide, and the like. Particularly preferred are 1,6-hexamethylenebis(N,N-dimethylhalocyanine), 4,4'-(methylenebis-p-phenylene)bis (N,N-di Methyl half-calendar).
「在末端具有N,N-二烷基半卡肼之聚合物」之較佳的具體實例係包括:例如,在經由以聚胺基甲酸酯彈性紗用 之抗氧化劑為眾所皆知的含有第三級氮之二醇及含有第三級氮之二胺與有機二異氰酸酯所製得之聚胺基甲酸酯或聚胺基甲酸酯-脲使其含有N,N-二烷基半卡肼末端基之聚合物等。在主鏈具有第三級氮,且在末端具有N,N-二烷基半卡肼之化合物係即使其為低濃度之N,N-二烷基半卡肼也能發揮在染色時的高耐熱性,可製得比未混合之情形時為高彈性回復性、高強伸度者。Preferred specific examples of the "polymer having an N,N-dialkylcarbazone at the end" include, for example, in the use of a polyurethane elastic yarn. The antioxidant is a well-known polycarbamate or polyurethane-urea prepared from a third-stage nitrogen-containing diol and a third-stage nitrogen-containing diamine and an organic diisocyanate. It contains a polymer of an N,N-dialkylhalfquinone terminal group or the like. A compound having a third-stage nitrogen in the main chain and having an N,N-dialkylhalf-carboxin at the end is capable of exhibiting a high dyeing even if it is a low concentration of N,N-dialkylcarbazone. The heat resistance can be made to be high elastic recovery and high tensile strength when it is not mixed.
該「含有第三級氮之二醇」之較佳的具體實例係包括:例如,可使用N-甲基-N,N-二乙醇胺、N-甲基-N,N-二丙醇胺、N-甲基-N,N-二異丙醇胺、N-丁基-N,N-二乙醇胺、N-三級-丁基-N,N-二乙醇胺(在下文中,簡稱為「TBDEA」。)、N-十八烷-N,N-二乙醇胺、N-苯甲基-N,N-二乙醇胺(在下文中,簡稱為「BDEA」。)、N-三級-丁基-N,N-二異丙醇胺,並且也可使用雙羥基乙基哌、雙羥基異丙基哌等之哌衍生物。其中,特佳的是TBDEA或BDEA。Preferred specific examples of the "third-stage nitrogen-containing diol" include, for example, N-methyl-N,N-diethanolamine, N-methyl-N,N-dipropanolamine, N-methyl-N,N-diisopropanolamine, N-butyl-N,N-diethanolamine, N-tertiary-butyl-N,N-diethanolamine (hereinafter, abbreviated as "TBDEA" .), N-octadecane-N,N-diethanolamine, N-benzyl-N,N-diethanolamine (hereinafter, abbreviated as "BDEA".), N-tertiary-butyl-N, N-diisopropanolamine, and bishydroxyethylperazine can also be used. Dihydroxyisopropyl piperazine Piper derivative. Among them, the most excellent one is TBDEA or BDEA.
「含有第三級氮之二胺」之較佳的具體實例係包括:例如,可使用N-甲基-3,3’-亞胺基雙(丙基胺)(在下文中,簡稱為「MIBPA」。)、N-丁基-胺基雙-丙基胺、N-甲基-胺基雙-乙基胺、N-三級-丁基-胺基雙-丙基胺、哌-N,N’-雙(3-胺基丙基)(在下文中,簡稱為「BAPP」。)、哌-N,N’-雙(2-胺基乙基)等。其中,特佳的是MIBPA或BAPP。Preferred specific examples of the "diamine containing a third-stage nitrogen" include, for example, N-methyl-3,3'-iminobis(propylamine) (hereinafter, simply referred to as "MIBPA"). N) butyl-amino bis-propylamine, N-methyl-amino bis-ethylamine, N-tertiary-butyl-amino bis-propylamine, piperazine -N,N'-bis(3-aminopropyl) (hereinafter, abbreviated as "BAPP".), piperazine -N,N'-bis(2-aminoethyl) and the like. Among them, the best one is MIBPA or BAPP.
有機二異氰酸酯之較佳的具體實例係例如可使用: PICM(亞甲基-雙(4-環己基異氰酸酯))、異佛酮二異氰酸酯(在下文中,簡稱為「IPDI」。)、離胺酸二異氰酸酯、由二聚酸衍生之DDI等之「脂肪族二異氰酸酯」等。其中,特佳的是PICM或IPDI。Preferred specific examples of the organic diisocyanate are, for example, usable: PICM (methylene-bis(4-cyclohexyl isocyanate)), isophorone diisocyanate (hereinafter, abbreviated as "IPDI"), "diamine diisocyanate, DDI derived from dimer acid, etc." Group diisocyanate" and the like. Among them, the best is PICM or IPDI.
並且,為與有機二異氰酸酯進行反應以形成末端半卡肼基,較佳為使用經取代之肼。「經取代之肼」之較佳的具體實例係包括:例如,可使用N,N-二甲基肼(在下文中,簡稱為「UDMH」。)、N,N-二乙基肼、N,N-二丙基肼、N,N-二異丙基肼、N,N-二丁基肼、N,N-二異丁基肼、N,N-二羥基乙基肼(在下文中,簡稱為「UDHEH」。)、N,N-二羥基異丙基肼等。其中,特佳的是UDMH或UDHEH。Further, in order to react with the organic diisocyanate to form a terminal halocenyl group, it is preferred to use a substituted anthracene. Preferred specific examples of the "substituted oxime" include, for example, N,N-dimethylhydrazine (hereinafter, abbreviated as "UDMH"), N,N-diethylhydrazine, N, N-dipropyl hydrazine, N,N-diisopropyl hydrazine, N,N-dibutyl fluorene, N,N-diisobutyl fluorene, N,N-dihydroxyethyl hydrazine (hereinafter, referred to as It is "UDHEH".), N,N-dihydroxyisopropyl hydrazine, and the like. Among them, the most excellent one is UDMH or UDHEH.
在聚胺基甲酸酯或聚胺基甲酸酯-脲使其含有N,N-二烷基半卡肼末端基之聚合物,較佳為藉由將異氰酸酯末端預聚合物與N,N-二烷基肼,在加入其他之鏈終止劑之前,已經添加完全化學計量之數量之肼以使其完全反應來調製。A polymer comprising an N,N-dialkylcarbazone terminal group in a polyurethane or a polyurethane-urea, preferably by reacting an isocyanate terminal prepolymer with N, N - Dialkyl hydrazine, which has been prepared by adding a stoichiometric amount of hydrazine to allow it to react completely before adding other chain terminators.
在末端具有N,N-二烷基半卡肼之聚合物之平均分子量較佳為1,000以上、20,000以下,此外,較佳為在每1公斤之在末端具有N,N-二烷基半卡肼之聚合物中,該半卡肼基係含有在0.1至100毫當量(meq/kg)之範圍。The average molecular weight of the polymer having an N,N-dialkylcarbazone at the end is preferably 1,000 or more and 20,000 or less. Further, it is preferred to have an N,N-dialkyl half card at the end per 1 kg. In the polymer of ruthenium, the semi-carboxy group is contained in the range of 0.1 to 100 milliequivalents (meq/kg).
其中,從均勻化聚胺基甲酸酯紗的原料紡絲液之黏度以獲得良好的可紡絲性的觀點來考慮,則較佳為將N,N-二烷基半卡肼末端基包含在聚胺基甲酸酯或聚胺基甲酸酯-脲 之聚合物。並且,為有效地發揮高紡絲速度、在染色時之耐熱性、對於不飽和脂肪酸之耐性、對於重金屬之耐性,雖然較佳為應使其含有多出某一程度的N,N-二烷基半卡肼化合物,但是從為獲得作為聚胺基甲酸酯紗之更良好的基本物性的觀點來考慮,則較佳為不要過多。一般而言,其含量較佳為在0.1重量%以上、6.0重量%以下之範圍。此外,該含量係根據用途而以預先試驗來適當地決定其最適值即可。Among them, from the viewpoint of homogenizing the viscosity of the raw material spinning solution of the polyurethane yarn to obtain good spinnability, it is preferred to contain the N,N-dialkylhalocyanine terminal group. In polyurethane or polyurethane-urea The polymer. Further, in order to effectively exhibit high spinning speed, heat resistance during dyeing, resistance to unsaturated fatty acids, and resistance to heavy metals, it is preferred to contain a certain amount of N,N-dioxane. The carbaryl compound is preferred, but it is preferably not excessive from the viewpoint of obtaining a more excellent basic physical property as a polyurethane yarn. In general, the content thereof is preferably in the range of 0.1% by weight or more and 6.0% by weight or less. Further, the content may be appropriately determined depending on the application in advance by an appropriate test.
並且,用以製得特別在高溫染色時之耐熱性之聚胺基甲酸酯彈性紗所需要之較佳的(b)化合物,係包括:將UDMH反應於經使TBDEA與PICM以加成聚合物計則為2:3至20:21之比率進行聚合所製得之聚胺基甲酸酯預聚合物的異氰酸酯末端,以使其形成二甲基半卡肼所獲得之化合物;或將UDMH反應於MIBPA與PICM之混合物與PICM係以2:3至20:21所組成之聚胺基甲酸酯-脲預聚合物之末端,以使其形成二甲基半卡肼所獲得之化合物。更進一步用以製得用於受到重複實施高溫染色製程的熱歷程之耐熱性聚胺基甲酸酯彈性紗,則較佳為N,N-二烷基半卡肼化合物係使用將單體型N,N-二烷基半卡肼之1,6-六亞甲基雙(N,N-二甲基半卡肼)、或4,4’-(亞甲基二-對-伸苯基)雙(N,N-二甲基半卡肼)併用於經將UDMH反應於由如前所述之TBDEA與PICM所構成之聚胺基甲酸酯之末端以使其形成二甲基半卡肼之化合物;或藉由將UDMH反應於由MIBPA與PICM之混合物與PICM所構成之聚胺基 甲酸酯-脲之末端以使其形成二甲基半卡肼之在末端具有N,N-二烷基半卡肼之聚合物,且在每1公斤紗中,含有半卡肼基為在0.1至200毫當量(meq/kg)之範圍。Further, a preferred compound (b) required for producing a polyurethane elastic yarn which is particularly resistant to heat resistance at high temperature dyeing comprises: reacting UDMH to an addition polymerization of TBDEA and PICM The compound is obtained by polymerizing the isocyanate end of the polyurethane prepolymer obtained by a ratio of 2:3 to 20:21 to form a compound obtained by dimethylhalocyanine; or UDMH The compound obtained by reacting a mixture of MIBPA and PICM with a PIMC series of a polyurethane-urea prepolymer having a composition of 2:3 to 20:21 to form a dimethylhalocyanine. Further, in order to obtain a heat-resistant polyurethane elastic yarn which is subjected to a heat history in which a high-temperature dyeing process is repeatedly performed, it is preferred to use a N,N-dialkylhalocyanine compound as a monomer type. 1,6-hexamethylenebis(N,N-dimethylhalocan) or 4,4'-(methylenedi-p-phenylene) of N,N-dialkylcarbazone Bis(N,N-dimethylsemicarbazide) and used to react UDMH to the end of a polyurethane composed of TBDEA and PICM as described above to form a dimethyl half card a compound of hydrazine; or a polyamine group consisting of a mixture of MIBPA and PICM and a PICM by reacting UDMH a terminal of a formate-urea such that it forms a dimethyl half-carbocyclic polymer having an N,N-dialkylcarbazone at the end, and contains a semi-carboxy group per 1 kg of yarn. A range of 0.1 to 200 milliequivalents (meq/kg).
在本發明使用之「(c)化合物」,亦即,「含氮芳香族化合物」係具有在分子內之芳香環配置氮原子的含氮芳香族雜環之化合物。其「化學結構骨架」係包括:具有含一氮之芳香族雜環之吡咯、吡啶、咔唑、喹啉;具有含二氮之芳香族雜環之咪唑、吡唑、嗒、吡、嘧啶、萘啶、啡啉;具有含三氮之芳香族雜環之三氮、苯并三唑、萘啶等,也可配置苯并噻唑或苯并噁唑等之氮以外的雜原子。此等含氮芳香族化合物之具體實例,較佳為作為紫外線吸收劑而為眾所皆知的苯并三唑化合物或三氮化合物,更具體言之,係包括:2-(3,5-二-三級-戊基-2-羥基苯基)苯并三唑、2-(3-三級-丁基-2-羥基苯基)-5-氯苯并三唑、2-(2-羥基-3,5-雙苯基)苯并三唑、2,4-二(2’,4’-二甲基苯基)-6-(2”-羥基-4”-烷氧基苯基)-1,3,5-三氮、2,2’-(1,4-伸苯基)雙〔4H-3,1-苯并噁-4-酮〕等之化合物。若以商品名列舉則係包括:汽巴嘉基股份有限公司(Ciba Geigy/Co.,Ltd.)製造之「TINUVIN」-P、「TINUVIN」-213、「TINUVIN」-234、「TINUVIN」-327、「TINUVIN」-328、「TINUVIN」-571;住友化學工業股份有限公司(Sumitomo Chemical Co.,Ltd.)製造之「Sumisorb」250;美國氰胺公司(American Cyanamid Co.)製造之「CYASORB」UV-5411、UV-1164、UV- 3638;旭電化工業股份有限公司(Asahi Denka Kogyo K.K.)製造之「ADEKASTAB」LA-31等。The "(c) compound" used in the present invention, that is, the "nitrogen-containing aromatic compound" is a compound having a nitrogen-containing aromatic heterocyclic ring in which a nitrogen atom is disposed in an aromatic ring in the molecule. The "chemical structure skeleton" includes: pyrrole having a nitrogen-containing aromatic heterocyclic ring, pyridine, oxazole, quinoline; imidazole, pyrazole, hydrazine having a dinitrogen-containing aromatic heterocyclic ring Pyr , pyrimidine, naphthyridine, phenanthroline; trinitrogen with an aromatic heterocycle containing trinitrogen A benzotriazole or a naphthyridine may be a hetero atom other than nitrogen such as benzothiazole or benzoxazole. Specific examples of such nitrogen-containing aromatic compounds are preferably benzotriazole compounds or trinitrogens which are well known as ultraviolet absorbers. The compounds, more specifically, include: 2-(3,5-di-tris-pentyl-2-hydroxyphenyl)benzotriazole, 2-(3-tris-butyl-2-hydroxyl) Phenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-bisphenyl)benzotriazole, 2,4-di(2',4'-dimethylphenyl) -6-(2"-hydroxy-4"-alkoxyphenyl)-1,3,5-triazole , 2,2'-(1,4-phenylene) bis[4H-3,1-benzaldehyde a compound such as 4-keto]. If listed under the trade name, it includes: "TINUVIN"-P, "TINUVIN"-213, "TINUVIN"-234, "TINUVIN" manufactured by Ciba Geigy/Co., Ltd. 327, "TINUVIN"-328, "TINUVIN"-571;"Sumisorb" 250 manufactured by Sumitomo Chemical Co., Ltd.; "CYASORB" manufactured by American Cyanamid Co. UV-5411, UV-1164, UV-3638; "ADEKASTAB" LA-31 manufactured by Asahi Denka Kogyo KK.
如上所述,欲製成能發揮在染色時之高耐熱性、對於不飽和脂肪酸之耐性、及對於重金屬之耐性,同時具有高彈性回復性及高強伸度之聚胺基甲酸酯彈性紗,則(c)化合物之含量必須為0.01重量%以上、0.30重量%以下。As described above, it is desired to produce a polyurethane elastic yarn which exhibits high heat resistance at the time of dyeing, resistance to unsaturated fatty acids, and resistance to heavy metals, and has high elastic recovery and high elongation. Then, the content of the compound (c) must be 0.01% by weight or more and 0.30% by weight or less.
(c)化合物係在如上所述者之中,從抑制紡絲中之揮發減量的觀點來考慮,則較佳為分子量為300以上之化合物族群。並且從為使在染色時之耐熱性及可紡絲性趨於良好的觀點來考慮,則更佳為在芳香環具有兩個以上氮原子之化合物。其係可視為由於容易形成與重金屬之錯合物而發揮螯合物功效之緣故。若欲更進一步充分發揮該功效時,則較佳為(c)含氮芳香族化合物之化學結構骨架為三氮。此外,(c)化合物之含量較佳為在0.01重量%以上、0.30重量%以下之範圍內,根據實際使用的(c)化合物之分子量與芳香環之有效氮數等或用途等而以預先試驗來適當地決定最適值。The compound (c) is a compound group having a molecular weight of 300 or more from the viewpoint of suppressing the amount of volatilization in spinning, as described above. Further, from the viewpoint of improving heat resistance and spinnability at the time of dyeing, a compound having two or more nitrogen atoms in the aromatic ring is more preferable. It can be considered that the chelate compound function is exhibited because it is easy to form a complex with a heavy metal. If the effect is to be further exerted, it is preferred that the chemical structure skeleton of the (c) nitrogen-containing aromatic compound is trinitrogen. . Further, the content of the compound (c) is preferably in the range of 0.01% by weight or more and 0.30% by weight or less, and is preliminarily tested according to the molecular weight of the compound (c) actually used, the effective nitrogen number of the aromatic ring, or the like. To properly determine the optimum value.
並且,欲製成特別具有染色時的高耐熱性之聚胺基甲酸酯彈性紗,則(c)化合物較佳為2,4-二(2’,4’-二甲基苯基)-6-(2”-羥基-4”-烷氧基苯基)-1,3,5-三氮。如前所述,(a)化合物則使用1,3,5-參(4-三級-丁基-3-羥基-2,6-二甲基苯甲基)-1,3,5-三氮-2,4,6(1H,3H,5H)-三酮,且使用2,4-二(2’,4’-二甲基苯基)-6-(2”-羥基-4”-烷氧基苯基)-1,3,5-三氮作為(c)化合物,藉此則可獲 得在染色時之耐熱性上特別高的增效功效。Further, in order to produce a polyurethane elastic yarn particularly having high heat resistance during dyeing, the compound (c) is preferably 2,4-bis(2',4'-dimethylphenyl)- 6-(2"-hydroxy-4"-alkoxyphenyl)-1,3,5-triazole . As mentioned above, the compound (a) uses 1,3,5-paran (4-tris-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-three. nitrogen -2,4,6(1H,3H,5H)-trione, and using 2,4-bis(2',4'-dimethylphenyl)-6-(2"-hydroxy-4"-alkane Oxyphenyl)-1,3,5-triazole As the compound (c), a synergistic effect which is particularly high in heat resistance at the time of dyeing can be obtained.
並且,作為(a)化合物、(b)化合物及(c)含氮芳香族化合物所使用之化合物,從例如加速對於聚胺基甲酸酯之分散及溶解、對於所製造之聚胺基甲酸酯紗賦予吾所欲之特性、並且可製成為適度的透明度之聚胺基甲酸酯紗、進一步即使在紡絲製程受到熱等時此等化合物之含量也不至於降低且不至於造成紗之變色等的觀點來考慮,則較佳為在20℃的N,N’-二甲基乙醯胺(在下文中,簡稱為「DMAc」)或DMF 20重量%溶液之黏度為10 cP以上、10,000 P以下的液體狀者。Further, as a compound used in the (a) compound, the (b) compound, and the (c) nitrogen-containing aromatic compound, for example, the dispersion and dissolution of the polyurethane are accelerated, and the produced polyaminocarboxylic acid is produced. The ester yarn imparts the desired characteristics and can be made into a moderately transparent polyurethane yarn, further reducing the content of such compounds even when the spinning process is subjected to heat, etc., and does not cause yarn From the viewpoint of discoloration and the like, it is preferred that N,N'-dimethylacetamide (hereinafter, abbreviated as "DMAc") at 20 ° C or a 20% by weight solution of DMF has a viscosity of 10 cP or more and 10,000. P liquid below P.
並且,在本發明所使用之聚胺基甲酸酯較佳為末端封鏈劑係使用一種或混合兩種以上者。「末端封鏈劑(end-capping agent)」較佳為:二甲基胺、二丙基胺、乙基甲基胺、二乙基胺、甲基丙基胺、異丙基甲基胺、二丙基胺、丁基甲基胺、異丁基甲基胺、異戊基甲基胺、二丁基胺、二戊基胺等之「一元胺」;乙醇、丙醇、丁醇、異丙醇、烯丙基醇、環戊醇等之「一元醇」;苯基異氰酸酯等之「一異氰酸酯」等。Further, the polyurethane used in the present invention is preferably one type or a mixture of two or more types of terminal blocking agents. The "end-capping agent" is preferably: dimethylamine, dipropylamine, ethylmethylamine, diethylamine, methylpropylamine, isopropylmethylamine, "monoamine" such as dipropylamine, butylmethylamine, isobutylmethylamine, isoamylmethylamine, dibutylamine, dipentylamine; ethanol, propanol, butanol, isopropanol, alkenyl "monohydric alcohol" such as propyl alcohol or cyclopentanol; "monoisocyanate" such as phenyl isocyanate.
此外,在本發明中,也可在不至於阻礙本發明之功效範圍內,在聚胺基甲酸酯彈性紗或聚胺基甲酸酯紡絲液中含有除了如前所述者以外之各種穩定劑,例如位阻型酚系、硫系、磷系等之「抗氧化劑」;位阻型胺系、三唑系、二苯甲酮系、苯甲酸酯系、鎳系、水楊基系等之「光穩定劑」;抗靜電劑、潤滑劑、過氧化物等之「分子調整劑」 ;金屬惰性化劑、有機及無機系之成核劑、中和劑、螢光增白劑、填料、難燃劑、難燃助劑、顏料等。例如,在耐光劑、抗氧化劑等含有2,6-二-三級-丁基-對-甲酚(BHT)或二苯甲酮系藥劑、各種位阻型胺系藥劑、氧化鐵、氧化鈦等之各種顏料、氧化鋅、氧化鈰、氧化鎂、碳黑等之無機物、氟系或聚矽氧系樹脂粉狀體、硬脂酸鎂等之金屬皂、含有銀或鋅或此等之化合物等之殺菌劑、消臭劑、防菌劑、聚矽氧或礦物油等之潤滑劑、硫酸鋇、氧化鈰、甜菜鹼或磷酸系等之各種的抗靜電劑等也是較佳,此外,將高分子與此等進行反應也是較佳。此外,從容易加速在乾式紡絲製程之紡絲速度的觀點來考慮,則可在紡絲原液中添加二氧化鈦、氧化鋅等之金屬氧化物微粒。此外,從提高耐熱性或功能性的觀點來考慮,也可在不至於阻礙本發明之功效範圍內添加無機物或無機多孔質(例如,竹炭、木炭、碳黑、多孔質泥、黏土、矽藻土、椰子殼活性炭、煤炭系活性炭、沸石、珠岩等)。Further, in the present invention, it is also possible to contain various kinds of polyurethane elastomer or polyurethane spinning solution in addition to those described above, without hindering the effects of the present invention. Stabilizers such as "antioxidants" such as sterically hindered phenolic, sulfuric, and phosphorus; sterically hindered amines, triazoles, benzophenones, benzoates, nickels, and salicyl "Light stabilizer" such as "molecular stabilizer" for antistatic agents, lubricants, peroxides, etc. Metal inerting agent, organic and inorganic nucleating agent, neutralizing agent, fluorescent whitening agent, filler, flame retardant, flame retardant, pigment, etc. For example, a light stabilizer, an antioxidant, or the like contains a 2,6-di-tertiary-butyl-p-cresol (BHT) or benzophenone-based agent, various hindered amine-based agents, iron oxide, and titanium oxide. Inorganic substances such as various pigments, zinc oxide, cerium oxide, magnesium oxide, carbon black, metal soaps such as fluorine-based or polyoxynoxy resin powders, magnesium stearate, and the like, containing silver or zinc or the like Other such as a fungicide, a deodorant, a fungicide, a lubricant such as polyoxymethylene or mineral oil, an antistatic agent such as barium sulfate, barium oxide, betaine or a phosphate system, etc., and the like, It is also preferred that the polymer reacts with these. Further, from the viewpoint of easily accelerating the spinning speed in the dry spinning process, metal oxide fine particles such as titanium oxide or zinc oxide can be added to the spinning dope. Further, from the viewpoint of improving heat resistance or functionality, it is also possible to add inorganic or inorganic porous substances (for example, bamboo charcoal, charcoal, carbon black, porous mud, clay, diatoms) without impeding the efficacy of the present invention. Earth, coconut shell activated carbon, coal-based activated carbon, zeolite, pearlite, etc.).
此等之其他之添加劑,也可在藉由聚胺基甲酸酯溶液與如前所述之改質劑的混合來調製紡絲原液時添加,此外,也可預先使其包含在混合前之聚胺基甲酸酯溶液中或分散液中。此等添加劑之含量係根據目的等來適當地決定。These other additives may also be added when the spinning dope is prepared by mixing the polyurethane solution with the modifier as described above, or may be included in advance before mixing. In the polyurethane solution or in the dispersion. The content of these additives is appropriately determined depending on the purpose and the like.
其次,就本發明之聚胺基甲酸酯彈性紗之製造方法詳加說明。Next, the manufacturing method of the polyurethane elastic yarn of the present invention will be described in detail.
在本發明較佳為首先製造聚胺基甲酸酯溶液。製造聚胺基甲酸酯溶液、或溶液中之溶質之聚胺基甲酸酯之方法 ,可為熔融聚合反應法、溶液聚合反應法中之任一、或其他之方法。然而,更佳為溶液聚合反應法。在溶液聚合反應法的情況,則由於在聚胺基甲酸酯產生凝膠等之異物少,因此容易紡絲、容易製造低纖度(fineness)之聚胺基甲酸酯紗。此外,在溶液聚合反應的情況,則有可省略製成為溶液之操作的優點。In the present invention, it is preferred to first produce a polyurethane solution. Method for producing a polyurethane solution, or a solute of a solute in a solution It may be any one of a melt polymerization method, a solution polymerization method, or the like. However, it is more preferred to be a solution polymerization method. In the case of the solution polymerization method, since a small amount of foreign matter such as a gel is generated in the polyurethane, it is easy to spin, and it is easy to produce a fine-density polyurethane yarn. Further, in the case of solution polymerization, there is an advantage that the operation of making a solution can be omitted.
並且,對於本發明特別適合之聚胺基甲酸酯係包括:藉由使用分子量為1,000以上、6,000以下之PTMG作為高分子二醇,使用MDI作為二異氰酸酯,且使用乙二醇、1,3-丙二醇、1,4-丁二醇、伸乙二胺、1,2-丙二胺、1,3-丙二胺中之至少一種作為鏈段增長劑所合成,且高溫側之熔點為在200℃以上、300℃以下之範圍者。Further, the polyurethane which is particularly suitable for the present invention includes: using PTMG having a molecular weight of 1,000 or more and 6,000 or less as a polymer diol, using MDI as a diisocyanate, and using ethylene glycol, 1, 3 - at least one of propylene glycol, 1,4-butanediol, ethylenediamine, 1,2-propylenediamine, and 1,3-propanediamine is synthesized as a segment growth agent, and the melting point of the high temperature side is 200 ° C or more, 300 ° C or less.
此等聚胺基甲酸酯係藉由例如在以DMAc、DMF、DMSO、NMP等或此等為主成份之溶劑中,使用如下所述之原料來合成即可製得。例如,在此等溶劑中加入各原料並使其溶解,並加熱至適當溫度使其進行反應以製成為聚胺基甲酸酯之所謂的「一步法(one-shot process)」。此外,將高分子二醇與二異氰酸酯首先使其熔融反應,然後將反應物溶解於溶劑,而使其與如前所述之鏈段增長劑之二醇等進行反應以製成為聚胺基甲酸酯之方法等係可採用之特別適合的方法。These polyurethanes can be obtained, for example, by synthesis using a raw material as described below in a solvent containing DMAc, DMF, DMSO, NMP or the like as a main component. For example, each raw material is added to these solvents and dissolved, and heated to a suitable temperature to carry out a reaction to form a so-called "one-shot process" of a polyurethane. Further, the polymer diol and the diisocyanate are first melt-reacted, and then the reactant is dissolved in a solvent to be reacted with a diol or the like of the chain extender as described above to prepare a polyamino group. A method of an acid ester or the like can be employed in a particularly suitable method.
若鏈段增長劑係使用低分子量二醇的情況,則欲使聚胺基甲酸酯之高溫側熔點達到200℃以上、300℃以下之範圍內之代表性方法係包括控制高分子二醇、MDI、低分子 量二醇之種類與比率之方法。例如,在高分子二醇之分子量為低的情況,則加以相對地增加MDI之比率,藉此則可製得高溫側之熔點為高之聚胺基甲酸酯。此外,同樣地,在低分子量二醇之分子量為低的情況,則加以相對地減少高分子二醇之比率,藉此則可製得高溫側之熔點為高之聚胺基甲酸酯。在高分子二醇之分子量為1,800以上的情況,若欲使高溫側之熔點為200℃以上,則較佳為以(MDI之莫耳數)/(高分子二醇之莫耳數)=1.5以上之比率進行聚合。When the segment growth agent is a low molecular weight diol, a representative method for the high temperature side melting point of the polyurethane to be in the range of 200 ° C or more and 300 ° C or less includes controlling the polymer diol, MDI, low molecular A method of measuring the type and ratio of diols. For example, when the molecular weight of the polymer diol is low, the ratio of MDI is relatively increased, whereby a high-melting-point polyurethane having a high melting point can be obtained. Further, similarly, when the molecular weight of the low molecular weight diol is low, the ratio of the high molecular weight diol is relatively reduced, whereby a polyurethane having a high melting point on the high temperature side can be obtained. When the molecular weight of the polymer diol is 1,800 or more, if the melting point of the high temperature side is 200 ° C or more, it is preferably (Mole of MDI) / (mole of polymer diol) = 1.5. The above ratios are aggregated.
此外,在合成此等聚胺基甲酸酯時,胺系觸媒或有機金屬觸媒等之觸媒較佳為使用一種或兩種以上混合使用。Further, in the case of synthesizing these polyurethanes, it is preferred to use one or a mixture of two or more kinds of catalysts such as an amine-based catalyst or an organic metal catalyst.
「胺系觸媒」係包括:例如,N,N-二甲基環己基胺、N,N-二甲基苯甲基胺、三乙基胺、N-甲基嗎啉、N-乙基嗎啉、N,N,N’,N’-四甲基伸乙二胺、N,N,N’,N’-四甲基-1,3-丙二胺、N,N,N’,N’-四甲基己二胺、雙-2-二甲基胺基乙基醚、N,N,N’,N’,N’-五甲基二伸乙三胺、四甲基胍、三伸乙二胺、N,N’-二甲基哌、N-甲基-N’-二甲基胺基乙基-哌、N-(2-二甲基胺基乙基)嗎啉、1-甲基咪唑、1,2-二甲基咪唑、N,N-二甲基胺基乙醇、N,N,N’-三甲基胺基乙基乙醇胺、N-甲基-N’-(2-羥基乙基)哌、2,4,6-參(二甲基胺基甲基)苯酚、N,N-二甲基胺基己醇、三乙醇胺等。The "amine-based catalyst" includes, for example, N,N-dimethylcyclohexylamine, N,N-dimethylbenzylamine, triethylamine, N-methylmorpholine, N-ethyl Morpholine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethyl-1,3-propanediamine, N,N,N', N'-tetramethylhexamethylenediamine, bis-2-dimethylaminoethyl ether, N,N,N',N',N'-pentamethyldiethylenetriamine, tetramethylguanidine, Tri-ethylenediamine, N,N'-dimethylper , N-methyl-N'-dimethylaminoethyl-peri , N-(2-dimethylaminoethyl)morpholine, 1-methylimidazole, 1,2-dimethylimidazole, N,N-dimethylaminoethanol, N,N,N'- Trimethylaminoethylethanolamine, N-methyl-N'-(2-hydroxyethyl)per 2,4,6-gin(dimethylaminomethyl)phenol, N,N-dimethylaminohexanol, triethanolamine, and the like.
此外,「有機金屬觸媒」係包括辛酸錫、二月桂酸二丁基錫、辛酸二丁基鉛等。Further, the "organometallic catalyst" includes tin octylate, dibutyltin dilaurate, and dibutyl lead octoate.
在藉由如上所述所製得之聚胺基甲酸酯溶液之聚胺基 甲酸酯之濃度通常較佳為在30重量%以上、80重量%以下之範圍。Polyamine group in a polyurethane solution prepared as described above The concentration of the formate is usually preferably in the range of 30% by weight or more and 80% by weight or less.
在本發明中,較佳為在此等聚胺基甲酸酯溶液中,將如前所述之(a)化合物、(b)化合物及(c)含氮芳香族化合物添加成符合預定之含量,以作為聚胺基甲酸酯紡絲溶液。(a)化合物、(b)化合物及(c)含氮芳香族化合物對於聚胺基甲酸酯溶液之添加方法係可採用任意方法。其代表性方法係可採用利用靜態混合器之方法、藉由攪拌之方法、利用均混機之方法、使用雙軸擠壓機之方法等之各種措施。然而,用於添加之(a)化合物、(b)化合物及(c)含氮芳香族化合物,從對於聚胺基甲酸酯溶液達成均勻添加的觀點來考慮,則較佳為製成為溶液來添加。In the present invention, it is preferred to add the compound (a), the compound (b) and the (c) nitrogen-containing aromatic compound as described above in a predetermined amount in the polyurethane solution. As a polyurethane spinning solution. The method of adding the compound (a), the compound (b), and (c) the nitrogen-containing aromatic compound to the polyurethane solution may be any method. The representative method is a method using a static mixer, a method of stirring, a method using a homomixer, a method using a twin-screw extruder, and the like. However, the (a) compound, the (b) compound, and the (c) nitrogen-containing aromatic compound are preferably prepared as a solution from the viewpoint of achieving uniform addition to the polyurethane solution. Add to.
此外,由於對於聚胺基甲酸酯溶液添加(a)化合物、(b)化合物及(c)含氮芳香族化合物,有可能導致造成添加後之混合溶液之溶液黏度,與添加前之聚胺基甲酸酯之溶液黏度相比較,將高於所預期的現象之情況。因此,從防止此現象的觀點來考慮,則較佳為將二甲基胺、二丙基胺、乙基甲基胺、二乙基胺、甲基丙基胺、異丙基甲基胺、二丙基胺、丁基甲基胺、異丁基甲基胺、異戊基甲基胺、二丁基胺、二戊基胺、等之「一元胺」;乙醇、丙醇、丁醇、異丙醇、烯丙基醇、環戊醇等之「一元醇」;苯基異氰酸酯等之「一異氰酸酯」等之末端封鏈劑係使用一種或兩種以上混合使用。Further, since the addition of the (a) compound, the (b) compound, and the (c) nitrogen-containing aromatic compound to the polyurethane solution may cause the solution viscosity of the mixed solution after the addition, and the polyamine before the addition. The viscosity of the solution of the carbamate will be higher than expected. Therefore, from the viewpoint of preventing this phenomenon, it is preferred to use dimethylamine, dipropylamine, ethylmethylamine, diethylamine, methylpropylamine, isopropylmethylamine, Dipropylamine, butylmethylamine, isobutylmethylamine, isoamylmethylamine, dibutylamine, dipentylamine, etc. "monoamine"; ethanol, propanol, butanol, isopropanol, The "monohydric alcohol" such as allyl alcohol or cyclopentanol; the terminal blocking agent such as "monoisocyanate" such as phenyl isocyanate may be used alone or in combination of two or more.
對於聚胺基甲酸酯溶液添加(a)化合物、(b)化合 物及(c)含氮芳香族化合物時,也可同時添加如前所述之例如耐光劑、抗氧化劑等之藥劑或顏料等。Adding (a) compound, (b) compound to the polyurethane solution When the compound (c) and the nitrogen-containing aromatic compound are added, a chemical agent such as a light stabilizer or an antioxidant, or a pigment may be added as described above.
並且,將此等聚胺基甲酸酯紡絲溶液加以紡絲,藉此可製得本發明之聚胺基甲酸酯彈性紗。Further, the polyurethane spinning solution is spun, whereby the polyurethane elastic yarn of the present invention can be obtained.
在本發明中,聚胺基甲酸酯彈性紗之纖度、單絲數、剖面形狀等係並無特殊的限制。例如,紗係也可為以1單絲所構成之單絲(monofilament),或以複數單絲所構成之複絲(multifilament)。紗之剖面形狀可為圓形、或扁平形。In the present invention, the fineness, the number of filaments, the cross-sectional shape, and the like of the polyurethane elastic yarn are not particularly limited. For example, the yarn system may be a monofilament composed of one monofilament or a multifilament composed of a plurality of monofilaments. The cross-sectional shape of the yarn may be round or flat.
並且,關於溶液紡絲之方式,也並無特殊限制,可適用任意方法,但是從欲能獲得紗表面為平滑,且高伸度、高回復性、高耐熱性之紗的觀點來考慮,則較佳為乾式紡絲。Further, the method of solution spinning is not particularly limited, and any method can be applied. However, from the viewpoint of obtaining a yarn having a smooth surface and high elongation, high recovery, and high heat resistance, Dry spinning is preferred.
此外,聚胺基甲酸酯彈性紗之殘留變形率(residual deformation ratio)(亦即定型性)與應力鬆弛率(stress relaxation ratio)之特性係容易受到在紡絲製程之條件、特別是導輥(godet roller)與捲取機之速度比的影響。因此,應根據紗之使用目的而適當地決定其速度比之條件。In addition, the residual deformation ratio (ie, the setting property) and the stress relaxation ratio of the polyurethane elastic yarn are susceptible to the conditions of the spinning process, particularly the guide rolls. (godet roller) and the speed ratio of the coiler. Therefore, the conditions of the speed ratio should be appropriately determined according to the purpose of use of the yarn.
亦即,從欲獲得具有吾所欲之殘留變形率與應力鬆弛率之聚胺基甲酸酯彈性紗的觀點來考慮,則較佳為導輥與捲取機之速度比為在1.15以上、1.65以下之範圍。並且,特別是欲獲得具有低殘留變形率及低應力鬆弛率之聚胺基甲酸酯彈性紗時,則導輥與捲取機之速度比更佳為在1.15以上、1.4以下之範圍,且進一步更佳為在1.15以上、 1.35以下之範圍。在另一方面,欲獲得具有高殘留變形率及高應力鬆弛率之聚胺基甲酸酯彈性紗時,則導輥與捲取機之速度比較佳為在1.25以上、1.65以下之範圍,且更佳為在1.35以上、1.65以下之範圍。That is, from the viewpoint of obtaining a polyurethane elastic yarn having a residual deformation ratio and a stress relaxation ratio which is desired, it is preferable that the speed ratio of the guide roller to the winder is 1.15 or more. The range below 1.65. Further, in particular, in order to obtain a polyurethane elastic yarn having a low residual deformation ratio and a low stress relaxation rate, the speed ratio of the guide roller to the winder is preferably in the range of 1.15 or more and 1.4 or less, and Further preferably more than 1.15, The range below 1.35. On the other hand, in order to obtain a polyurethane elastic yarn having a high residual deformation ratio and a high stress relaxation rate, the speed of the guide roller and the winder is preferably in the range of 1.25 or more and 1.65 or less, and More preferably, it is in the range of 1.35 or more and 1.65 or less.
此外,由於藉由提高紡絲速度,則可提高聚胺基甲酸酯彈性紗之強度,若採用450公尺/分鐘以上之紡絲速度時,則可製得在實務應用上具有適當的強度水準之彈性紗,因此為較佳。並且,若考慮及工業生產時,則較佳為在約450至1,000公尺/分鐘之紡絲速度。In addition, since the strength of the polyurethane elastic yarn can be increased by increasing the spinning speed, if a spinning speed of 450 m/min or more is used, an appropriate strength can be obtained in practical applications. A standard elastic yarn is therefore preferred. Further, it is preferably a spinning speed of about 450 to 1,000 meters per minute in consideration of industrial production.
茲將本發明以實施例更詳加以說明。The invention will be described in more detail by way of examples.
茲將本發明之聚胺基甲酸酯彈性紗之斷裂強度、斷裂伸度、殘留變形率、應力鬆弛率、在染色時之耐熱性、顯示一般耐熱性之外觀品質、熱軟化點等之測定法加以說明。The breaking strength, elongation at break, residual deformation ratio, stress relaxation rate, heat resistance at the time of dyeing, appearance quality showing general heat resistance, and thermosoftening point of the polyurethane elastic yarn of the present invention are measured. The law is explained.
〈殘留變形率、應力鬆弛率、斷裂強度、斷裂伸度〉 殘留變形率、應力鬆弛率、斷裂強度、斷裂伸度,係將聚胺基甲酸酯彈性紗使用INSTRON 5564型拉伸試驗機實施拉伸試驗來測定。<Residual deformation rate, stress relaxation rate, breaking strength, elongation at break> The residual deformation rate, the stress relaxation rate, the breaking strength, and the elongation at break were measured by performing a tensile test using a INSTRON Model 5564 tensile tester.
將試料長度為5公分(L1)之試料以50公分/分鐘之拉伸速率反復5次加以300%伸長,並假設在第5次的300%伸長時之應力為(G1)。其次,試料之長度仍以經300%伸長之狀態保持30秒鐘。假設保持30秒鐘後之應力為(G2)。其次,回復試料之伸長並假設應力成為0時的 試料之長度為(L2)。反復進行該300%伸張、保持及回復之操作,且在第6次之伸張則伸長至試料切斷為止。假設該斷裂時之應力為(G3)、斷裂時之試料長度為(L3)。在下文中,如上所述之特性係可以如下所述之式計算得:斷裂強度(cN)=(G3);應力鬆弛率(%)=100×((G1)-(G2))/(G1);殘留變形率(%)=100×((L2)-(L1))/(L1);斷裂伸度(%)=100×((L3)-(L1))/(L1)。The sample having a sample length of 5 cm (L1) was subjected to 300% elongation by 5 times at a tensile rate of 50 cm/min, and the stress at the 300% elongation at the 5th time was assumed to be (G1). Secondly, the length of the sample was maintained at 300% elongation for 30 seconds. Assume that the stress after 30 seconds is maintained as (G2). Second, return the elongation of the sample and assume that the stress becomes zero. The length of the sample is (L2). The 300% stretching, holding, and recovery operations were repeated, and the stretching was performed until the sample was cut at the sixth stretch. It is assumed that the stress at the time of the fracture is (G3), and the length of the sample at the time of the fracture is (L3). Hereinafter, the characteristics as described above can be calculated as follows: breaking strength (cN) = (G3); stress relaxation rate (%) = 100 × ((G1) - (G2)) / (G1) ; residual deformation rate (%) = 100 × ((L2) - (L1)) / (L1); elongation at break (%) = 100 × ((L3) - (L1)) / (L1).
〈在染色時之耐熱性1(染色溫度較低之耐綸混用布帛在附著不飽和脂肪酸與重金屬的狀態下之耐性)〉 以一般針織(knitting)方法製造由85重量%之東麗工業股份有限公司(Toray Industries,Inc.)製造之耐綸長纖維(24 dtex(分特)、7絲(filament))與15重量%之聚胺基甲酸酯彈性紗(20 dtex)所構成之機上經圈(wale)數為11/英寸(11/2.54公分)、機上緯圈(course)數為25/英寸(25/2.54公分)之兩路進線半平經編組織(two-way half tricot stitch),以作為針織坯布(knitted raw fabric)。<Heat resistance at the time of dyeing 1 (resistance of a nylon-mixed fabric having a low dyeing temperature in a state in which unsaturated fatty acids and heavy metals are attached) Polyamide long fibers (24 dtex, 7 filaments) and 15% by weight manufactured by Toray Industries, Inc., manufactured by Toray Industries, Inc., were manufactured by a general knitting method. The polyurethane warp yarn (20 dtex) consists of a machine with a wale of 11/inch (11/2.54 cm) and a course of 25/inch (25/). Two-way half tricot stitches of 2.54 cm) are used as knitted raw fabrics.
將所製得之針織坯布在170℃、60秒鐘、3%伸長下之條件下加以預定型,接著塗布0.1毫升之藥劑1,接著(大致同時、或在1分鐘以內)塗布0.1毫升之藥劑2後, 實施乾熱處理(經175℃、60秒鐘之乾熱處理後,暫時取出並散熱至室溫後,在180℃、60秒鐘實施乾熱處理),其次,則以縱橫兩方向交替最大20%之伸長、2次/秒鐘之彎曲試驗機進行試驗。此外,藥劑1係使用含有1%油酸之礦物油系耐綸用紡絲油劑。藥劑2則使用醋酸銅水溶液(銅濃度為100 ppm)。經如上所述所附著藥劑1及藥劑2之針織坯布,係以典型案例方式加以再現在染色前之階段的耐綸系伸縮性針織坯布則有微量的針織時之機械油(有金屬份混入)與耐綸用紡絲油劑附著之情形者,且相對於0.9克之針織坯布的藥劑1之附著量為3.0毫克、藥劑2之附著量則為3.0毫克。The prepared knitted fabric was pre-formed under the conditions of 170 ° C, 60 seconds, 3% elongation, and then 0.1 ml of the drug 1 was applied, followed by coating (about substantially simultaneously, or within 1 minute) 0.1 ml of the drug. After 2, Perform dry heat treatment (after 175 ° C, dry heat treatment for 60 seconds, temporarily take out and dissipate heat to room temperature, dry heat treatment at 180 ° C for 60 seconds), and secondly, alternate 20% elongation in both vertical and horizontal directions. The test was performed with a bending tester of 2 times/second. Further, the pharmaceutical 1 is a mineral oil-based nylon spinning oil containing 1% oleic acid. For the drug 2, an aqueous copper acetate solution (copper concentration of 100 ppm) was used. The knitted fabric of the drug 1 and the drug 2 adhered as described above is reproduced in a typical case. The nylon-based stretchable knitted fabric at the stage before dyeing has a small amount of mechanical oil (with metal mixed) during knitting. In the case where the nylon was adhered to the spin finish, the amount of adhesion to the drug 1 of 0.9 g of the knitted fabric was 3.0 mg, and the amount of the drug 2 was 3.0 mg.
將所製得之伸縮性布帛以慣用方法加以染色。亦即,將1.0% owf(按織物重量:on weight of fabric)之Kayanol Milling Blue 2RW(日本化藥股份有限公司(Nippon Kayaku Co.,Ltd.)製造)之染色液,在98℃以液流染色法加以染色。The obtained stretchable fabric was dyed by a conventional method. That is, a dyeing solution of 1.0% owf (by weight of fabric) of Kayanol Milling Blue 2RW (manufactured by Nippon Kayaku Co., Ltd.) at a flow rate of 98 ° C Dyeing by staining.
以目視或加以擴大後,觀察在所製得之染色伸縮性布帛之聚胺基甲酸酯組織之損傷程度,並以下列基準判斷。此外,判斷係由5人參與,並使用最頻值(最多出現的判斷)。若判斷結果分歧為2人、2人、1人時,則判斷為「△」。After visual observation or enlargement, the degree of damage of the polyurethane structure of the dyed stretch fabric produced was observed and judged on the following basis. In addition, the judgment is made by 5 people and the most frequent value (the most frequently occurring judgment) is used. If the result of the judgment is 2, 2, or 1 person, it is judged as "△".
A:無損傷;B:坯布觀察到彈性喪失、凹陷現象,若放大觀察時,則聚胺基甲酸酯彈性紗已經脆化; C:布帛有穿洞。A: no damage; B: loss of elasticity and depression phenomenon observed on the grey fabric, and if enlarged, the polyurethane elastic yarn has been embrittled; C: There is a hole in the cloth.
〈在染色時之耐熱性2(染色溫度較低的耐綸混用布帛對於反復進行染色之耐性)〉 為評估將聚胺基甲酸酯紗加以高溫染色時之耐熱老化性而實施將聚胺基甲酸酯紗以下列方法加以高溫液處理之試驗。並且,就在該高溫液處理之前後之聚胺基甲酸酯紗測定斷裂強度,並計算得其保持率。<Heat resistance at the time of dyeing 2 (resistance of nylon mixed fabric with low dyeing temperature for repeated dyeing)> In order to evaluate the heat aging resistance when the polyurethane yarn was subjected to high temperature dyeing, a test for subjecting the polyurethane yarn to a high temperature liquid treatment in the following manner was carried out. Further, the breaking strength was measured for the polyurethane yarn after the high temperature liquid treatment, and the retention ratio was calculated.
將聚胺基甲酸酯紗在100%伸長狀態下加以固定,並施加預定型(170℃、60秒鐘)後,以無張緊狀態在室溫下放置24小時,然後以與如前所述之方法相同方式測定斷裂強度(G3)。並且,加以預定型之後,仍在其固定狀態下封入於裝有98℃高溫水之壓力容器內,並以98℃、60分鐘之處理為一套而總共實施三次之在高溫液中之處理。此時,在第一次高溫液中處理之後、第二次高溫液中處理之後,則各自暫時從壓力容器取出試料,並使其散熱至室溫後,施加其次之高溫液中處理。由壓力容器取出第三次高溫液中處理後之聚胺基甲酸酯紗,使其成為無張緊狀態在室溫下放置24小時,然後以與如前所述之方法相同的方式測定斷裂強度(G5)。計算得相對於僅施加預定型之紗的斷裂強度(G3)的經第三次高溫液中處理後之紗的斷裂強度(G5)之比率(斷裂強度保持率),以作為耐熱性2之指標:斷裂強度保持率(%)=100×(G5)/(G3)。The polyurethane yarn was fixed in a state of 100% elongation, and after applying a predetermined type (170 ° C, 60 seconds), it was left untensioned at room temperature for 24 hours, and then as before. The method described is used to determine the breaking strength (G3) in the same manner. Further, after the predetermined type was applied, it was sealed in a pressure vessel containing 98 ° C of high-temperature water in a fixed state, and treated in a high-temperature liquid for a total of three times in a set of 98 ° C for 60 minutes. At this time, after the treatment in the first high temperature liquid and after the second high temperature liquid treatment, the samples are temporarily taken out from the pressure vessel, and are allowed to dissipate heat to room temperature, and then applied to the next high temperature liquid. The polyurethane film treated in the third high temperature liquid was taken out from the pressure vessel, allowed to stand in an untensioned state at room temperature for 24 hours, and then the fracture was measured in the same manner as described above. Strength (G5). The ratio (breaking strength retention ratio) of the rupture strength (G5) of the yarn after the treatment in the third high-temperature liquid with respect to the breaking strength (G3) of only the predetermined type of yarn is calculated as an index of heat resistance 2 : breaking strength retention ratio (%) = 100 × (G5) / (G3).
〈在染色時之耐熱性3(染色溫度較高的聚酯混用布帛在 附著不飽和脂肪酸與重金屬的狀態下之耐性)〉 以一般針織方法製造由82重量%之東麗工業股份有限公司製造之聚對苯二甲酸乙二醇酯長纖維(filament)(33 dtex、48絲)與18重量%之聚胺基甲酸酯彈性紗(22 dtex)所構成之機上經圈數為13/英寸(13/2.54公分)、機上緯圈數為30/英寸(30/2.54公分)之兩路進線半平經編組織,以作為針織坯布。<The heat resistance at the time of dyeing 3 (the polyester mixed fabric with a higher dyeing temperature is in the Resistance to unsaturated fatty acids and heavy metals) Polyethylene terephthalate filament (33 dtex, 48 filament) manufactured by Toray Industries, Inc., 82% by weight, and 18% by weight of polyurethane were produced by a general knitting method. The elastic yarn (22 dtex) consists of two lines of semi-finished warp knitting with 13/inch (13/2.54 cm) and 30/inch (30/2.54 cm) weft on the machine. As a knitted fabric.
將所製得之針織坯布在190℃、60秒鐘、3%伸長下之條件下加以預定型,接著塗布0.1毫升之藥劑1,接著(大致同時或在1分鐘以內),塗布0.1毫升之藥劑2後,實施乾熱處理(在195℃、60秒鐘之乾熱處理後,暫時取出並散熱至室溫後,在200℃、60秒鐘實施乾熱處理),其次,則在用於縱橫兩方向交替最大20%之伸長、2次/秒鐘之彎曲試驗機進行試驗。此外,藥劑1係使用含有1%油酸之礦物油系聚酯用紡絲油劑。藥劑2則使用酯酸銅水溶液(銅濃度為100 ppm)。藉由如上所述所附著藥劑1及藥劑2之針織坯布,係以典型案例方式加以再現於染色前之階段的耐綸系伸縮性針織坯布則有微量的針織時之機械油(有金屬份混入)與耐綸用紡絲油劑附著之情形者,且相對於1.0克之針織坯布的藥劑1之附著量為3.0毫克、藥劑2之附著量則為3.0毫克。The prepared knitted fabric was preliminarily prepared under the conditions of 190 ° C, 60 seconds, and 3% elongation, and then 0.1 ml of the drug 1 was applied, followed by (substantially simultaneously or within 1 minute), and 0.1 ml of the drug was applied. 2, after the dry heat treatment (after 195 ° C, 60 seconds of dry heat treatment, temporarily taken out and cooled to room temperature, dry heat treatment at 200 ° C, 60 seconds), and then used in the vertical and horizontal directions The test was carried out with a bending tester of up to 20% elongation and 2 times/second. Further, as the drug 1, a spinning oil agent for mineral oil-based polyester containing 1% oleic acid is used. For the drug 2, an aqueous solution of copper citrate (copper concentration of 100 ppm) was used. The knitted fabric of the drug 1 and the drug 2 adhered as described above is a mechanically stretched nylon fabric which is reproduced in a typical case before the dyeing process, and has a slight amount of mechanical oil (when metal is mixed). When it is adhered to the spinning oil agent for nylon, the adhesion amount to the drug 1 of 1.0 g of the knitted fabric is 3.0 mg, and the adhesion amount of the drug 2 is 3.0 mg.
將所製得之伸縮性布帛,以慣用方法加以染色。亦即,以含有4% owf之高能量型分散染料「Dianix」Black HG-FS conc(德司達公司(Dystar Textilfarben GmbH)製 造)、及1% owf之POE烷基胺醚型硫酸酯(硫酸化)「NEWBON WS」(日華化學股份有限公司(Nicca Chemical Co.,Ltd.)製造之均染劑(levelling agent)),且藉由酯酸與醋酸鈉之緩衝液調整成pH 5之染浴,在125℃染色60分鐘。The obtained stretchable fabric was dyed by a conventional method. That is, the high-energy disperse dye "Dianix" Black HG-FS conc (made by Dystar Textilfarben GmbH) containing 4% owf Manufactured, and 1% owf of POE alkylamine ether sulfate (sulfated) "NEWBON WS" (a levelling agent manufactured by Nicca Chemical Co., Ltd.) And dyeing to a pH 5 dye bath by a buffer of ester acid and sodium acetate, and dyeing at 125 ° C for 60 minutes.
接著,以含有2克/公升之低亞硫酸鈉(保險粉;hydrosulfite)、特殊陰離子系界面活性劑「Senkanol CW」(Senka Co.Ltd.製造之皂洗劑(soaping agent))、及1克/公升之氫氧化鈉之處理浴,在70℃實施還原洗淨20分鐘。Next, it contains 2 g/L of low sodium sulfite (hydrosulfite), a special anionic surfactant "Senkanol CW" (soaping agent manufactured by Senka Co. Ltd.), and 1 g/liter. The sodium hydroxide treatment bath was subjected to reduction washing at 70 ° C for 20 minutes.
以目視或加以放大後,觀察在所製得之染色伸縮性布帛之聚胺基甲酸酯組織之損傷程度,並以下列基準判斷。此外,判斷係由5人參與,並使用最頻值(最多出現的判斷)。若判斷結果分歧為2人、2人、1人時,則判斷為「△」。After visual observation or amplification, the degree of damage of the polyurethane structure of the dyed stretch fabric produced was observed and judged on the following basis. In addition, the judgment is made by 5 people and the most frequent value (the most frequently occurring judgment) is used. If the result of the judgment is 2, 2, or 1 person, it is judged as "△".
A:無損傷;B:坯布觀察到彈性喪失、凹陷現象,放大觀察時,聚胺基甲酸酯彈性紗則已脆化;C:布帛有穿洞。A: no damage; B: loss of elasticity and sag phenomenon observed on the grey cloth, when the magnified observation, the polyurethane elastic yarn is already embrittled; C: the cloth has a through hole.
〈在染色時之耐熱性4(染色溫度較高的聚酯混用布帛對於反復進行染色之耐性)〉 為評估將聚胺基甲酸酯紗加以高溫染色時之耐熱老化性,將聚胺基甲酸酯紗以如下所述之方法實施高溫液處理。並且,針對在該高溫液處理之前後的聚胺基甲酸酯紗測 定其斷裂強度,並計算得其之保持率。<Heat resistance at the time of dyeing 4 (resistance of repeated dyeing of polyester mixed fabrics with higher dyeing temperature) In order to evaluate the heat aging resistance when the polyurethane yarn was subjected to high temperature dyeing, the polyurethane yarn was subjected to a high temperature liquid treatment as described below. And, for the polyurethane yarn after the high temperature liquid treatment Determine the breaking strength and calculate the retention rate.
將聚胺基甲酸酯紗在100%伸長狀態下加以固定,並施加預定型(190℃、60秒鐘)後,以無張緊狀態在室溫下放置24小時,然後以與如前所述之方法相同方式測定斷裂強度(G3)。並且,加以預定型之後,仍在其固定狀態下封入於裝有130℃高溫水之壓力容器內,並以130℃、60分鐘之處理為一套而總共實施三次之在高溫液中處理。此時,在第一次高溫液中處理之後、第二次高溫液中處理之後,則各自暫時從壓力容器取出試料,並使其散熱至室溫後,施加其次之高溫液中處理。由壓力容器取出第三次高溫液中處理後之聚胺基甲酸酯紗,使其成為無張緊狀態,在室溫下放置24小時,然後以與如前所述之方法相同的方式測定斷裂強度(G5)。計算得相對於僅施加預定型之紗的斷裂強度(G3)的經第三次高溫液中處理後之紗的斷裂強度(G5)之比率(斷裂強度保持率),以作為耐熱性4之指標:斷裂強度保持率(%)=100×(G5)/(G3)。The polyurethane yarn was fixed in a state of 100% elongation, and after applying a predetermined type (190 ° C, 60 seconds), it was left untensioned at room temperature for 24 hours, and then as before. The method described is used to determine the breaking strength (G3) in the same manner. Further, after the predetermined type was applied, it was sealed in a pressure vessel containing 130 ° C of high-temperature water in a fixed state, and treated in a high-temperature liquid for three times in total at 130 ° C for 60 minutes. At this time, after the treatment in the first high temperature liquid and after the second high temperature liquid treatment, the samples are temporarily taken out from the pressure vessel, and are allowed to dissipate heat to room temperature, and then applied to the next high temperature liquid. The polyurethane film treated in the third high temperature liquid was taken out from the pressure vessel to make it untensioned, left at room temperature for 24 hours, and then measured in the same manner as described above. Breaking strength (G5). The ratio (breaking strength retention ratio) of the rupture strength (G5) of the yarn after the treatment in the third high-temperature liquid with respect to the breaking strength (G3) of only the predetermined type of yarn is calculated as an index of heat resistance 4 : breaking strength retention ratio (%) = 100 × (G5) / (G3).
〈外觀品質〉 除了在如前所述之染色時之耐熱性1之試驗、或染色時之耐熱性3之試驗中,並未實施藥劑1及藥劑2之塗布及彎曲試驗以外,其餘則以相同的方式製造染色伸縮性布帛。亦即,製成為針織坯布後,施加預定型、乾熱處理、染色處理,以製造染色伸縮性布帛。就所製得之染色伸縮性布帛(寬度為1.8公尺、長度約20公尺之布匹),以目 視檢查坯布外觀,放大觀察聚胺基甲酸酯組織,並以下列基準進行判斷:此外,判斷係由5人參與,並使用最頻值(最多出現的判斷)。若判斷結果分歧為2人、2人、1人時,則判斷為「△」。<Appearance quality> In the test of heat resistance 1 at the time of dyeing as described above or the heat resistance 3 at the time of dyeing, dyeing was performed in the same manner except that the coating and bending tests of the drug 1 and the drug 2 were not carried out. Flexible fabric. That is, after the knitted fabric is produced, a predetermined type, a dry heat treatment, and a dyeing treatment are applied to produce a dyed stretch fabric. For the dyed stretch fabric (width of 1.8 meters, length of about 20 meters), The appearance of the grey fabric was examined, and the polyurethane structure was magnified and judged on the following basis: In addition, the judgment was carried out by 5 persons, and the most frequent value (the most frequently judged) was used. If the result of the judgment is 2, 2, or 1 person, it is judged as "△".
A:無波紋(waviness)或條紋狀缺點,組織也為均質;B:有局部性的波紋或條紋狀缺點,且每20公尺為一處以下;C:有波紋或條紋狀缺點,且每20公尺為一處以上。A: no waviness or streaky defect, the structure is also homogeneous; B: has local corrugation or stripe-like defects, and is less than one place every 20 meters; C: has ripple or stripe defects, and each 20 meters is more than one place.
〈熱軟化點〉 測定熱軟化點以作為聚胺基甲酸酯紗的熱定型性指標之一。聚胺基甲酸酯彈性紗係使用Rheometric Scientific,Inc.製造之動態彈性率測定機RSAII,以10℃/分鐘之升溫速度實施測定動態儲存彈性模數(dynamic storage elastic modulus)E’之溫度分布。熱軟化點係由在E’曲線為在80℃以上、130℃以下的平坦區域下之切線、與在160℃以上E’由於熱軟化而降低的E’曲線之切線的交點測定。此外,E’係使用對數軸,溫度係使用線性軸。<thermal softening point> The thermal softening point was measured as one of the heat setting indexes of the polyurethane yarn. The polyurethane elastic yarn was subjected to measurement of the temperature distribution of the dynamic storage elastic modulus E' at a temperature increase rate of 10 ° C/min using a dynamic elastic modulus measuring machine RSAII manufactured by Rheometric Scientific, Inc. . The thermal softening point is measured by the intersection of a tangent line in a flat region of 80 ° C or more and 130 ° C or less in the E' curve, and a tangent to the E' curve which is lowered by heat softening at 160 ° C or higher. In addition, E' uses a logarithmic axis and temperature uses a linear axis.
(各化合物之含量) 準備1克之紗試料,裝入於以二氯甲烷作為溶劑之索格利特萃取器(Soxhlet’s extractor)加以萃取60分鐘以上,暫時將萃取液加以乾固,其次,使用甲醇以相同的方式加以萃取,然後將各化合物以高性能液相層析法(HPLC )加以離析。以1 HNMR等之慣用方法決定其結構,使用該經離析、決定結構之各化合物以高性能液相層析法預先量測,並以下式計算其含率:含率(重量%)=(試料波峰面積/量測波峰面積)×(量測試料重量/紗試料重量)。(Content of each compound) One gram of the yarn sample was prepared and charged in a Soxhlet's extractor using methylene chloride as a solvent for extraction for 60 minutes or more, and the extract was temporarily dried, and then methanol was used. The extraction was carried out in the same manner, and then each compound was isolated by high performance liquid chromatography (HPLC). The structure is determined by a conventional method such as 1 H NMR, and each of the isolated and determined structures is preliminarily measured by high performance liquid chromatography, and the content is calculated by the following formula: content (% by weight) = (sample) Crest area/measured peak area) × (quantity test material weight / yarn sample weight).
以慣用方法實施來自於分子量為2,900之PTMG、MDI及乙二醇之聚合,以製備聚胺基甲酸酯聚合物之DMAc溶液(35重量%)。將此作為高分子溶液A1。Polymerization of PTMG, MDI and ethylene glycol having a molecular weight of 2,900 was carried out by a conventional method to prepare a DMAc solution (35 wt%) of a polyurethane resin. This was taken as the polymer solution A1.
其次,(a)位阻型酚系化合物、(b)N,N-二烷基半卡肼化合物、及(c)含氮芳香族化合物係分別使用(a1)1,3,5-參(4-三級-丁基-3-羥基-2,6-二甲基苯甲基)-1,3,5-三氮-2,4,6(1H,3H,5H)-三酮、(b1)具有TBDEA與PICM之6至8之重覆數的加成物,且與UDMH反應以在末端形成二甲基半卡肼之聚合物、(c1)2,4-二(2’,4’-二甲基苯基)-6-(2”-羥基-4”-烷氧基苯基)-1,3,5-三氮(分子量為509;CYTEC Industries Inc.製造之「Cyasorb」(註冊商標)UV-1164),並將此等以2.0:3.0:0.1之比率混合,然後調製其之DMAc溶液(35重量%)。該溶液之調製係使用水平磨WILLY A.BACHOFEN公司製造之DYNO-MIL KDL,以填充85%之氧化鋯珠粒,且在50克/分鐘之流速的條件下,使各成份均勻溶解於DMAc。將此溶液作為添加劑溶液B1。Next, (a) a hindered phenol compound, (b) an N,N-dialkylhalocyanine compound, and (c) a nitrogen-containing aromatic compound are respectively used as (a1) 1,3,5-para ( 4-tertiary-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazole -2,4,6(1H,3H,5H)-trione, (b1) an adduct having a repeat number of 6 to 8 of TBDEA and PICM, and reacting with UDMH to form a dimethyl half card at the end Polymer of ruthenium, (c1) 2,4-bis(2',4'-dimethylphenyl)-6-(2"-hydroxy-4"-alkoxyphenyl)-1,3,5 - three nitrogen (Molecular weight: 509; "Cyasorb" (registered trademark) UV-1164, manufactured by CYTEC Industries Inc.), and these were mixed at a ratio of 2.0:3.0:0.1, and then a DMAc solution (35 wt%) thereof was prepared. The solution was prepared by horizontally grinding DYNO-MIL KDL manufactured by WILLY A. BACHOFEN Co., Ltd. to fill 85% of zirconia beads, and the components were uniformly dissolved in DMAc at a flow rate of 50 g/min. This solution was used as the additive solution B1.
將高分子溶液A1、添加劑溶液B1分別以94.9重量% 及5.1重量%之比率均勻混合,以作為紡絲溶液D1。The polymer solution A1 and the additive solution B1 were respectively 94.9% by weight. And the ratio of 5.1% by weight was uniformly mixed to serve as the spinning solution D1.
將該紡絲溶液D1在設定導輥與捲取機之速度比為1.40、且以540公尺/分鐘之紡絲速度實施乾式紡絲並加以捲取,以製造20 dtex、單絲之聚胺基甲酸酯彈性紗(200克之紗線捲裝(yarn package))。用於構成所製得之聚胺基甲酸酯彈性紗的各成份之組成(重量%)係如表1所示,(a)化合物、(b)化合物及(c)含氮芳香族化合物係分別含有2.0重量%、3.0重量%及0.1重量%。The spinning solution D1 was dry-spun at a spinning speed of 1.40 at a set guide roller and a coiler, and was taken up at a spinning speed of 540 m/min to produce a 20 dtex, monofilament polyamine. Carbamate elastic yarn (200 g yarn package). The composition (% by weight) of each component constituting the obtained polyurethane elastic yarn is as shown in Table 1, (a) compound, (b) compound, and (c) nitrogen-containing aromatic compound system. It is contained in an amount of 2.0% by weight, 3.0% by weight, and 0.1% by weight, respectively.
然後,測定該聚胺基甲酸酯彈性紗之斷裂伸度、斷裂強度、殘留變形率、應力鬆弛率、熱軟化點,並展示於表2。Then, the elongation at break, the breaking strength, the residual deformation ratio, the stress relaxation rate, and the thermal softening point of the polyurethane elastic yarn were measured and shown in Table 2.
從所製得之聚胺基甲酸酯彈性紗(20 dtex)與東麗工業股份有限公司製造之耐綸長纖維(24 dtex、7絲),以一般針織方法製造由85重量%之耐綸長纖維與15重量%之聚胺基甲酸酯彈性紗所構成之機上經圈數為11/英寸、機上緯圈數為25/英寸之兩路進線半平經編組織,以作為針織坯布(耐綸系伸縮性布帛)。就該針織坯布,實施在染色時之耐熱性1之試驗,評估在附著不飽和脂肪酸與重金屬時之染色時之耐熱性。此外,將其針織坯布加以染色後評估其外觀品質。From the obtained polyurethane elastic yarn (20 dtex) and nylon long fiber (24 dtex, 7 filament) manufactured by Toray Industries Co., Ltd., manufactured by a general knitting method, made of 85% by weight of nylon Long-fiber and 15% by weight of polyurethane elastic yarns are machined on a machine with a number of turns of 11/inch and a machine with a number of laps of 25/inch. Grey fabric (Nylon-based stretch fabric). In the knitted fabric, the heat resistance 1 at the time of dyeing was carried out, and the heat resistance at the time of dyeing the unsaturated fatty acid and the heavy metal was evaluated. In addition, the knitted fabric was dyed and evaluated for its appearance quality.
並且,就所製得之聚胺基甲酸酯彈性紗在反復進行染色時之耐熱性,以在染色時之耐熱性2之試驗來加以評估。Further, the heat resistance of the obtained polyurethane elastic yarn when it was repeatedly dyed was evaluated by the test of heat resistance 2 at the time of dyeing.
聚胺基甲酸酯彈性紗之斷裂伸度、斷裂強度、殘留變 形率、應力鬆弛率、及熱定型性之指標的熱軟化點係皆為與未混合(b)化合物、(c)化合物之比較例1(如後所述)相同,且在加工性或坯布特性方面並未觀察到混合此等之添加劑的不良影響。Breaking elongation, breaking strength and residual change of polyurethane elastic yarn The thermosoftening point of the index of shape rate, stress relaxation rate, and heat setting property is the same as that of Comparative Example 1 (described later) of the unmixed (b) compound and the compound (c), and is in processability or gray cloth. The adverse effects of mixing such additives have not been observed in terms of properties.
此外,耐綸系伸縮性布帛在染色時之耐熱性,包括在染色時之耐熱性1(對於不飽和脂肪酸與重金屬之耐性)、在染色時之耐熱性2(對於反復進行染色之耐性)在內皆比比較例1顯現出大幅度地提高。並且,經染色所製得之伸縮性布帛係無缺點,且為具有優越的外觀品質者。In addition, the heat resistance of the nylon-based stretchable fabric at the time of dyeing includes heat resistance 1 at the time of dyeing (resistance to unsaturated fatty acids and heavy metals), heat resistance at the time of dyeing 2 (resistance to repeated dyeing) The internal comparison of Comparative Example 1 showed a significant increase. Further, the stretchable fabric obtained by dyeing has no defects and is excellent in appearance quality.
(a)化合物、(b)化合物及(c)含氮芳香族化合物係分別使用(a1)1,3,5-參(4-三級-丁基-3-羥基-2,6-二甲基苯甲基)-1,3,5-三氮-2,4,6(1H,3H,5H)-三酮、及(a2)二乙烯基苯與對-甲酚之加成聚合物(杜邦公司(E.I.du Pont de Nemours and Company)製造之「Methacrol」(註冊商標)2390)、在實施例1所使用之(b1)具有TBDEA與PICM之6至8之重覆數的加成物,且與UDMH進行反應以在末端形成二甲基半卡肼之聚合物、以及(c1)2,4-二(2’,4’-二甲基苯基)-6-(2”-羥基-4”-烷氧基苯基)-1,3,5-三氮,並將此等以1.0:1.0:3.0:0.15之比率混合,然後調製其之DMAc溶液(35重量%)。該溶液之調製係使用水平磨WILLY A.BACHOFEN公司製造之DYNO-MIL KDL,以填充85%之氧化鋯珠粒,且在50克/分鐘之流速的條件下,使各成份均勻溶解於DMAc。將此溶液作 為添加劑溶液B2。(a) a compound, (b) a compound, and (c) a nitrogen-containing aromatic compound are respectively used (a1) 1,3,5-paran (4-tris-butyl-3-hydroxy-2,6-dimethyl Benzomethyl)-1,3,5-triazole -2,4,6(1H,3H,5H)-trione, and (a2) an addition polymer of divinylbenzene and p-cresol (Methacrol, manufactured by EI du Pont de Nemours and Company) (registered trademark) 2390), (b1) an adduct having a repeat number of 6 to 8 of TBDEA and PICM used in Example 1, and reacting with UDMH to form a dimethyl semi-carbosome at the end Polymer, and (c1) 2,4-bis(2',4'-dimethylphenyl)-6-(2"-hydroxy-4"-alkoxyphenyl)-1,3,5 - three nitrogen And these were mixed at a ratio of 1.0:1.0:3.0:0.15, and then a DMAc solution (35 wt%) thereof was prepared. The solution was prepared by horizontally grinding DYNO-MIL KDL manufactured by WILLY A. BACHOFEN Co., Ltd. to fill 85% of zirconia beads, and the components were uniformly dissolved in DMAc at a flow rate of 50 g/min. This solution was used as the additive solution B2.
將在實施例1所調製之高分子溶液A1、如上所述之添加劑溶液B2分別以94.85重量%及5.15重量%之比率均勻混合,以作為紡絲溶液D2。The polymer solution A1 prepared in Example 1 and the additive solution B2 as described above were uniformly mixed at a ratio of 94.85% by weight and 5.15% by weight, respectively, to obtain a spinning solution D2.
將該紡絲溶液D2在設定導輥與捲取機之速度比為1.40、及以540公尺/分鐘之紡絲速度實施乾式紡絲並加以捲取,以製造20 dtex、單絲之聚胺基甲酸酯彈性紗(200克之紗線捲裝)。用於構成所製得之聚胺基甲酸酯彈性紗的各成份之組成(重量%)係如表1所示,(a)化合物、(b)化合物及(c)含氮芳香族化合物係分別含有2.0重量%、3.0重量%及0.15重量%。The spinning solution D2 was dry-spun and coiled at a spinning speed of 1.40 and a spinning speed of 540 m/min to produce a 20 dtex, monofilament polyamine. Carbide elastomer yarn (200 g yarn package). The composition (% by weight) of each component constituting the obtained polyurethane elastic yarn is as shown in Table 1, (a) compound, (b) compound, and (c) nitrogen-containing aromatic compound system. It is contained in an amount of 2.0% by weight, 3.0% by weight, and 0.15% by weight, respectively.
從所製得之聚胺基甲酸酯彈性紗(20 dtex)與東麗工業股份有限公司製造之耐綸長纖維(24 dtex、7絲)製造與實施例1之情形相同之兩路進線半平經編組織,以作為針織坯布(耐綸系伸縮性布帛)。就該針織坯布,實施在染色時之耐熱性1之試驗,評估在附著不飽和脂肪酸與重金屬時之染色時之耐熱性。此外,將其針織坯布加以染色後評估其外觀品質。Two lines of the same line as in the case of Example 1 were produced from the obtained polyurethane elastic yarn (20 dtex) and the nylon long fiber (24 dtex, 7 wire) manufactured by Toray Industries, Ltd. Semi-warp warp organization for use as a knitted fabric (Nylon-based stretch fabric). In the knitted fabric, the heat resistance 1 at the time of dyeing was carried out, and the heat resistance at the time of dyeing the unsaturated fatty acid and the heavy metal was evaluated. In addition, the knitted fabric was dyed and evaluated for its appearance quality.
並且,就所製得之聚胺基甲酸酯彈性紗在反復進行染色時之耐熱性,以在染色時之耐熱性2之試驗來加以評估。Further, the heat resistance of the obtained polyurethane elastic yarn when it was repeatedly dyed was evaluated by the test of heat resistance 2 at the time of dyeing.
該聚胺基甲酸酯彈性紗之斷裂伸度、斷裂強度、殘留變形率、應力鬆弛率、及熱定型性之指標的熱軟化點,係皆與未混合(b)化合物、(c)化合物之比較例1(如後 所述)相同,且在加工性或坯布特性方面,並未觀察到經混合此等之添加劑所引起之不良影響。The thermal softening point of the elongation, fracture strength, residual deformation rate, stress relaxation rate, and heat setting property of the polyurethane elastic yarn is both unmixed (b) compound and (c) compound Comparative example 1 (as after The) is the same, and in terms of processability or fabric properties, no adverse effects caused by mixing the additives are observed.
此外,耐綸系伸縮性布帛在染色時之耐熱性,包括在染色時之耐熱性1(對於不飽和脂肪酸與重金屬之耐性)、在染色時之耐熱性2(對於反復進行染色之耐性)在內皆比比較例1顯現出大幅度地提高。並且,經染色所製得之伸縮性布帛係無缺點,且為具有優越的外觀品質者。In addition, the heat resistance of the nylon-based stretchable fabric at the time of dyeing includes heat resistance 1 at the time of dyeing (resistance to unsaturated fatty acids and heavy metals), heat resistance at the time of dyeing 2 (resistance to repeated dyeing) The internal comparison of Comparative Example 1 showed a significant increase. Further, the stretchable fabric obtained by dyeing has no defects and is excellent in appearance quality.
將分子量為1,800之PTMG、MDI、伸乙二胺、及末端封鏈劑之二乙基胺以慣用方法進行聚合,並製備聚胺基甲酸酯-脲聚合物之DMAc溶液(35重量%)。將此作為高分子溶液A2。The PTMG, MDI, ethylenediamine, and terminal chain-blocking diethylamine having a molecular weight of 1,800 were polymerized by a conventional method, and a DMAc solution of a polyurethane-urea polymer (35 wt%) was prepared. . This was taken as the polymer solution A2.
其次,(a)化合物、(b)化合物及(c)含氮芳香族化合物係分別使用(a1)1,3,5-參(4-三級-丁基-3-羥基-2,6-二甲基苯甲基)-1,3,5-三氮-2,4,6(1H,3H,5H)-三酮、及(a2)二乙烯基苯與對-甲酚之加成聚合物(杜邦公司製造之「Methacrol」(註冊商標)2390)、在實施例1所使用之(b1)具有TBDEA與PICM之6至8之重覆數的加成物,且與UDMH進行反應以在末端形成二甲基半卡肼之聚合物、以及(c1)2,4-二(2’,4’-二甲基苯基)-6-(2”-羥基-4”-烷氧基苯基)-1,3,5-三氮,並將此等以1.0:1.0:3.0:0.10之比率混合,然後調製其之DMAc溶液(35重量%)。該溶液之調製係使用水平磨WILLY A.BACHOFEN公司製造之DYNO-MIL KDL,以填充85%之氧 化鋯珠粒,且在50克/分鐘之流速的條件下,使各成份均勻溶解於DMAc。將此溶液作為添加劑溶液B3。Next, (a) a compound, (b) a compound, and (c) a nitrogen-containing aromatic compound are respectively used as (a1) 1,3,5-paran (4-tris-butyl-3-hydroxy-2,6-). Dimethylbenzyl)-1,3,5-triazole -2,4,6(1H,3H,5H)-trione, and (a2) an addition polymer of divinylbenzene and p-cresol ("Methacrol" (registered trademark) 2390, manufactured by DuPont), (b1) an adduct having a repeat number of 6 to 8 of TBDEA and PICM used in Example 1, and reacting with UDMH to form a polymer of dimethylhalocyanine at the terminal, and (c1) 2,4-bis(2',4'-dimethylphenyl)-6-(2"-hydroxy-4"-alkoxyphenyl)-1,3,5-triazo And these were mixed at a ratio of 1.0:1.0:3.0:0.10, and then a DMAc solution (35 wt%) thereof was prepared. The solution was prepared by horizontally grinding DYNO-MIL KDL manufactured by WILLY A. BACHOFEN Co., Ltd. to fill 85% of zirconia beads, and the components were uniformly dissolved in DMAc at a flow rate of 50 g/min. This solution was used as the additive solution B3.
將高分子溶液A2、添加劑溶液B3分別以94.9重量%及5.1重量%之比率均勻混合,以作為紡絲溶液D3。將該紡絲溶液D3在設定導輥與捲取機之速度比為1.20、及以600公尺/分鐘之紡絲速度實施乾式紡絲並加以捲取,以製造22 dtex、2絲(filament)之複絲(multifilament)之聚胺基甲酸酯彈性紗(500克之紗線捲裝)。用於構成所製得之聚胺基甲酸酯彈性紗的各成份之組成(重量%)係如表1所示,(a)化合物、(b)化合物及(c)含氮芳香族化合物係分別含有2.0重量%、3.0重量%及0.1重量%。The polymer solution A2 and the additive solution B3 were uniformly mixed at a ratio of 94.9 wt% and 5.1 wt%, respectively, to obtain a spinning solution D3. The spinning solution D3 was dry-spun and wound up at a speed ratio of 1.20 and a spinning speed of 600 m/min to produce 22 dtex and 2 filaments. Polyfilament elastic yarn of a multifilament (500 g yarn package). The composition (% by weight) of each component constituting the obtained polyurethane elastic yarn is as shown in Table 1, (a) compound, (b) compound, and (c) nitrogen-containing aromatic compound system. It is contained in an amount of 2.0% by weight, 3.0% by weight, and 0.1% by weight, respectively.
以一般針織方法從所製得之聚胺基甲酸酯彈性紗(22 dtex)與東麗工業股份有限公司製造之聚對苯二甲酸乙二醇酯長纖維(33 dtex、48絲),製造由82重量%之聚對苯二甲酸乙二醇酯長纖維與18重量%之聚胺基甲酸酯彈性紗所構成之機上經圈數為13/英寸、機上緯圈數為30/英寸之兩路進線半平經編組織,以作為針織坯布(聚酯系伸縮性布帛)。就該針織坯布,實施在染色時之耐熱性3之試驗,評估在附著不飽和脂肪酸與重金屬時之染色時之耐熱性。此外,將其針織坯布加以染色後評估其外觀品質。Manufactured from the obtained polyurethane elastic yarn (22 dtex) and polyethylene terephthalate long fiber (33 dtex, 48 filament) manufactured by Toray Industries Co., Ltd. by a general knitting method. The number of on-machine passes consisting of 82% by weight of polyethylene terephthalate long fibers and 18% by weight of polyurethane elastic yarn is 13/inch, and the number of on-board laps is 30/ The two-inch in-line half-warp warp organization is used as a knitted fabric (polyester-based stretch fabric). With respect to the knitted fabric, a test for heat resistance 3 at the time of dyeing was carried out, and heat resistance at the time of dyeing with unsaturated fatty acid and heavy metal was evaluated. In addition, the knitted fabric was dyed and evaluated for its appearance quality.
並且,將就所製得之聚胺基甲酸酯彈性紗在反復進行染色時之耐熱性,以在染色時之耐熱性4之試驗加以評估。Further, the heat resistance of the obtained polyurethane elastic yarn upon repeated dyeing was evaluated by a test for heat resistance 4 at the time of dyeing.
該聚胺基甲酸酯彈性紗之斷裂伸度、斷裂強度、殘留 變形率、應力鬆弛率、及熱定型性之指標的熱軟化點,係皆與未混合(b)化合物、(c)化合物等之比較例2(如後所述)相同,且在加工性或坯布特性方面,並未觀察到經混合此等之添加劑所引起之不良影響。Breaking elongation, breaking strength, residue of the polyurethane elastic yarn The thermal softening points of the indexes of the deformation rate, the stress relaxation rate, and the heat setting property are the same as those of Comparative Example 2 (described later) in which the compound (b), the compound (c), and the like are not mixed, and are in processability or In terms of the characteristics of the fabric, no adverse effects caused by the mixing of the additives were observed.
此外,聚酯系伸縮性布帛在染色時之耐熱性,係在染色時之耐熱性3(對於不飽和脂肪酸與重金屬之耐性),連同在染色時之耐熱性4(對於反復進行染色之耐性),皆比比較例2顯現出大幅度地提高。並且,經染色所製得之伸縮性布帛係無缺點,且為具有優越的外觀品質者。In addition, the heat resistance of the polyester-based stretch fabric at the time of dyeing is heat resistance 3 at the time of dyeing (resistance to unsaturated fatty acids and heavy metals), together with heat resistance at the time of dyeing 4 (resistance to repeated dyeing) Both showed a significant improvement over Comparative Example 2. Further, the stretchable fabric obtained by dyeing has no defects and is excellent in appearance quality.
(a)化合物、(b)化合物及(c)含氮芳香族化合物係分別使用在實施例2使用之(a2)二乙烯基苯與對-甲酚之加成聚合物(杜邦公司製造之「Methacrol」(註冊商標)2390)、及(a3)三甘醇-雙〔3-(3-三級-丁基-5-甲基-4-經基苯基)丙酸酯〕、在實施例1所使用之(b1)具有TBDEA與PICM之6至8之重覆數的加成物,且與UDMH進行反應以在末端形成二甲基半卡肼之聚合物、及(b2)4,4’-(亞甲基二-對-伸苯基)雙(N,N-二甲基半卡肼)、以及(c1)2,4-二(2’,4’-二甲基苯基)-6-(2”-羥基-4”-烷氧基苯基)-1,3,5-三氮,並將此等以1.0:1.0:2.0:0.5:0.1之比率混合,然後調製其之DMAc溶液(35重量%)。該溶液之調製係使用水平磨WILLY A.BACHOFEN公司製造之DYNO-MIL KDL,以填充85%之氧化鋯珠粒,且在50克/分鐘之流速的條件下,使各成份均 勻溶解於DMAc。將此溶液作為添加劑溶液B4。(a) a compound, (b) a compound, and (c) a nitrogen-containing aromatic compound are each used in the addition polymer of (a2) divinylbenzene and p-cresol used in Example 2 (made by DuPont). Methacrol" (registered trademark) 2390), and (a3) triethylene glycol-bis[3-(3-tris-butyl-5-methyl-4-phenylphenyl)propionate], in the examples (b1) an adduct having a repeat number of 6 to 8 of TBDEA and PICM, and reacting with UDMH to form a polymer of dimethylhalocyanine at the end, and (b2)4,4 '-(Methylene di-p-phenylene) bis(N,N-dimethylhalocyanine), and (c1) 2,4-di(2',4'-dimethylphenyl) -6-(2"-hydroxy-4"-alkoxyphenyl)-1,3,5-triazole And these were mixed at a ratio of 1.0:1.0:2.0:0.5:0.1, and then a DMAc solution (35 wt%) thereof was prepared. The solution was prepared by horizontally grinding DYNO-MIL KDL manufactured by WILLY A. BACHOFEN Co., Ltd. to fill 85% of zirconia beads, and the components were uniformly dissolved in DMAc at a flow rate of 50 g/min. This solution was used as the additive solution B4.
將在實施例3所調製之高分子溶液A2、如上所述之添加劑溶液B4分別以95.4重量%及4.6重量%之比率均勻混合,以作為紡絲溶液D4。The polymer solution A2 prepared in Example 3 and the additive solution B4 as described above were uniformly mixed at a ratio of 95.4% by weight and 4.6% by weight, respectively, to obtain a spinning solution D4.
將該紡絲溶液D4在設定導輥與捲取機之速度比為1.20、及以600公尺/分鐘之紡絲速度實施乾式紡絲並加以捲取,以製造22 dtex、2絲之複絲之聚胺基甲酸酯彈性紗(500克之紗線捲裝)。The spinning solution D4 was dry-spun at a speed ratio of 1.20 and a spinning speed of 600 m/min at a spinning speed of the set guide roller and the coiler to produce a 22 dtex, 2 filament multifilament. Polyurethane elastomer yarn (500 g yarn package).
用於構成所製得之聚胺基甲酸酯彈性紗的各成份之組成(重量%)係如表1所示,(a)化合物、(b)化合物及(c)含氮芳香族化合物係分別含有2.0重量%、2.5重量%及0.1重量%。The composition (% by weight) of each component constituting the obtained polyurethane elastic yarn is as shown in Table 1, (a) compound, (b) compound, and (c) nitrogen-containing aromatic compound system. It is contained in an amount of 2.0% by weight, 2.5% by weight, and 0.1% by weight, respectively.
從所製得之聚胺基甲酸酯彈性紗(22 dtex)與東麗工業股份有限公司製造之聚對苯二甲酸乙二醇酯長纖維(33 dtex、48絲)製造與實施例3之情形相同之兩路進線半平經編組織,以作為針織坯布(聚酯系伸縮性布帛)。就該針織坯布,實施在染色時之耐熱性3之試驗,評估在附著不飽和脂肪酸與重金屬時之染色時之耐熱性。此外,將其針織坯布加以染色後評估其外觀品質。Manufactured from the obtained polyurethane elastic yarn (22 dtex) and polyethylene terephthalate long fiber (33 dtex, 48 filament) manufactured by Toray Industries, Ltd. and Example 3 In the same situation, the two lines of the line are semi-finished and warp-knitted as a knitted fabric (polyester-based stretch fabric). With respect to the knitted fabric, a test for heat resistance 3 at the time of dyeing was carried out, and heat resistance at the time of dyeing with unsaturated fatty acid and heavy metal was evaluated. In addition, the knitted fabric was dyed and evaluated for its appearance quality.
並且,將就所製得之聚胺基甲酸酯彈性紗在反復進行染色時之耐熱性,以在染色時之耐熱性4之試驗加以評估。Further, the heat resistance of the obtained polyurethane elastic yarn upon repeated dyeing was evaluated by a test for heat resistance 4 at the time of dyeing.
該聚胺基甲酸酯彈性紗之斷裂伸度、斷裂強度、殘留變形率、應力鬆弛率、及熱定型性之指標的熱軟化點,係 皆與未混合(b)化合物、(c)化合物之比較例2(如後所述)相同,且在加工性或坯布特性方面,並未觀察到經混合此等之添加劑所引起之不良影響。The thermal softening point of the elongation, fracture strength, residual deformation rate, stress relaxation rate, and heat setting property of the polyurethane elastic yarn is Both of them were the same as Comparative Example 2 (described later) in which the (b) compound and the compound (c) were not mixed, and no adverse effects caused by mixing the additives were observed in terms of processability or fabric properties.
此外,聚酯系伸縮性布帛在染色時之耐熱性,係在染色時之耐熱性3(對於不飽和脂肪酸與重金屬之耐性),連同在染色時之耐熱性4(對於反復進行染色之耐性),皆比比較例2顯現出大幅度地提高。並且,經加以染色所製得之伸縮性織物係無缺點,且具有優越的外觀品質者。In addition, the heat resistance of the polyester-based stretch fabric at the time of dyeing is heat resistance 3 at the time of dyeing (resistance to unsaturated fatty acids and heavy metals), together with heat resistance at the time of dyeing 4 (resistance to repeated dyeing) Both showed a significant improvement over Comparative Example 2. Further, the stretchable fabric obtained by dyeing is not disadvantageous and has superior appearance quality.
(a)化合物、(b)化合物及(c)含氮芳香族化合物係分別使用在實施例2使用之(a2)二乙烯基苯與對-甲酚之加成聚合物(杜邦公司製造之「Methacrol」(註冊商標)2390)、(a3)三甘醇-雙〔3-(3-三級-丁基-5-甲基-4-羥基苯基)丙酸酯〕、及(a4)伸乙基-1,2-雙(3,3-雙〔3-三級-丁基-4-羥基苯基〕丁酸酯)、在實施例4使用之(b2)4,4’-(亞甲基二-對-伸苯基)雙(N,N-二甲基半卡肼)、以及(c1)2,4-二(2’,4’-二甲基苯基)-6-(2”-羥基-4”-烷氧基苯基)-1,3,5-三氮,並將此等以1.0:1.0:1.0:1.5:0.1之比率混合,然後調製其之DMAc溶液(35重量%)。該溶液之調製係使用水平磨WILLY A.BACHOFEN公司製造之DYNO-MIL KDL,以填充85%之氧化鋯珠粒,且在50克/分鐘之流速的條件下,使各成份均勻溶解於DMAc。將此溶液作為添加劑溶液B5。並且,除了如上所述之外,作為穩定劑而將藉由三級-丁基二乙醇胺 與亞甲基-雙(4-環己基異氰酸酯)之反應所形成之聚胺基甲酸酯(杜邦公司製造之「Methacrol」(註冊商標)2462)之DMAc溶液(濃度35重量%),作為其他之添加劑溶液Z1(35重量%)來使用。(a) a compound, (b) a compound, and (c) a nitrogen-containing aromatic compound are each used in the addition polymer of (a2) divinylbenzene and p-cresol used in Example 2 (made by DuPont). Methacrol" (registered trademark) 2390), (a3) triethylene glycol-bis[3-(3-tris-butyl-5-methyl-4-hydroxyphenyl)propionate], and (a4) Ethyl-1,2-bis(3,3-bis[3-tris-butyl-4-hydroxyphenyl]butyrate), used in Example 4 (b2) 4,4'- (Asia Methyl di-p-phenylene) bis(N,N-dimethylhalocyanine), and (c1) 2,4-di(2',4'-dimethylphenyl)-6-( 2"-hydroxy-4"-alkoxyphenyl)-1,3,5-triazole And these were mixed at a ratio of 1.0:1.0:1.0:1.5:0.1, and then a DMAc solution (35 wt%) thereof was prepared. The solution was prepared by horizontally grinding DYNO-MIL KDL manufactured by WILLY A. BACHOFEN Co., Ltd. to fill 85% of zirconia beads, and the components were uniformly dissolved in DMAc at a flow rate of 50 g/min. This solution was used as the additive solution B5. And, in addition to the above, a polyurethane formed by the reaction of tris-butyldiethanolamine and methylene-bis(4-cyclohexyl isocyanate) as a stabilizer (DuPont) The DMAc solution (concentration: 35 wt%) of "Methacrol" (registered trademark) 2462) was used as another additive solution Z1 (35 wt%).
將在實施例3所調製之高分子溶液A2、如上所述之添加劑溶液B5及其他之添加劑溶液Z1分別以93.4重量%、4.6重量%及2.0重量%之比率均勻混合,以作為紡絲溶液D5。The polymer solution A2 prepared in Example 3, the additive solution B5 as described above, and the other additive solution Z1 were uniformly mixed at a ratio of 93.4% by weight, 4.6% by weight, and 2.0% by weight, respectively, as a spinning solution D5. .
將該紡絲溶液D5在設定導輥與捲取機之速度比為1.20、及以600公尺/分鐘之紡絲速度實施乾式紡絲並加以捲取,以製造22 dtex、2絲之複絲之聚胺基甲酸酯彈性紗(500克之紗線捲裝)。The spinning solution D5 was dry-spun at a speed ratio of 1.20 at a set guide roller and a coiler, and was taken up at a spinning speed of 600 meters/minute to produce a 22 dtex, 2 wire multifilament. Polyurethane elastomer yarn (500 g yarn package).
用於構成所製得之聚胺基甲酸酯彈性紗的各成份之組成(重量%)係如表1所示,(a)化合物、(b)化合物及(c)含氮芳香族化合物係分別含有3.0重量%、1.5重量%及0.1重量%。The composition (% by weight) of each component constituting the obtained polyurethane elastic yarn is as shown in Table 1, (a) compound, (b) compound, and (c) nitrogen-containing aromatic compound system. It contained 3.0% by weight, 1.5% by weight, and 0.1% by weight, respectively.
從所製得之聚胺基甲酸酯彈性紗(22 dtex)與東麗工業股份有限公司製造之聚對苯二甲酸乙二醇酯長纖維(33 dtex、48絲)製造與實施例3之情形相同之兩路進線半平經編組織,以作為針織坯布(聚酯系伸縮性布帛)。就該針織坯布,實施在染色時之耐熱性3之試驗,評估在附著不飽和脂肪酸與重金屬時之染色時之耐熱性。此外,將其針織坯布加以染色後評估其外觀品質。Manufactured from the obtained polyurethane elastic yarn (22 dtex) and polyethylene terephthalate long fiber (33 dtex, 48 filament) manufactured by Toray Industries, Ltd. and Example 3 In the same situation, the two lines of the line are semi-finished and warp-knitted as a knitted fabric (polyester-based stretch fabric). With respect to the knitted fabric, a test for heat resistance 3 at the time of dyeing was carried out, and heat resistance at the time of dyeing with unsaturated fatty acid and heavy metal was evaluated. In addition, the knitted fabric was dyed and evaluated for its appearance quality.
並且,將就所製得之聚胺基甲酸酯彈性紗在反復進行 染色時之耐熱性,以在染色時之耐熱性4之試驗加以評估。And, the polyurethane elastic yarn obtained will be repeated The heat resistance at the time of dyeing was evaluated by the test of heat resistance 4 at the time of dyeing.
該聚胺基甲酸酯彈性紗之斷裂伸度、斷裂強度、殘留變形率、應力鬆弛率、及熱定型性之指標的熱軟化點,係皆與未混合(b)化合物、(c)化合物之比較例2(如後所述)相同,且在加工性或坯布特性方面,並未觀察到經混合此等之添加劑所引起之不良影響。The thermal softening point of the elongation, fracture strength, residual deformation rate, stress relaxation rate, and heat setting property of the polyurethane elastic yarn is both unmixed (b) compound and (c) compound Comparative Example 2 (described later) was the same, and in terms of processability or fabric properties, no adverse effects caused by mixing such additives were observed.
此外,聚酯系伸縮性布帛在染色時之耐熱性,係在染色時之耐熱性3(對於不飽和脂肪酸與重金屬之耐性),連同在染色時之耐熱性4(對於反復進行染色之耐性),皆比比較例2顯現出大幅度地提高。並且,經加以染色所製得之伸縮性織物係無缺點,且具有優越的外觀品質者。In addition, the heat resistance of the polyester-based stretch fabric at the time of dyeing is heat resistance 3 at the time of dyeing (resistance to unsaturated fatty acids and heavy metals), together with heat resistance at the time of dyeing 4 (resistance to repeated dyeing) Both showed a significant improvement over Comparative Example 2. Further, the stretchable fabric obtained by dyeing is not disadvantageous and has superior appearance quality.
(a)化合物、(b)化合物及(c)含氮芳香族化合物係分別使用在實施例2使用之(a2)二乙烯基苯與對-甲酚之加成聚合物(杜邦公司製造之「Methacrol」(註冊商標)2390)、(a3)三甘醇-雙〔3-(3-三級-丁基-5-甲基-4-羥基苯基)丙酸酯〕、及(a4)伸乙基-1,2-雙(3,3-雙〔3-三級-丁基-4-羥基苯基〕丁酸酯)、在實施例1所使用之(b1)具有TBDEA與PICM之6至8之重覆數的加成物,且與UDMH進行反應以在末端形成二甲基半卡肼之聚合物、及在實施例4使用之(b2)4,4’-(亞甲基二-對-伸苯基)雙(N,N-二甲基半卡肼)、以及(c1)2,4-二(2’,4’-二甲基苯基)-6-(2”-羥基-4”-烷氧基苯基)-1,3,5-三氮,並將此等以1.0:2.0:0.5:2.0:0.5:0.1之比率混合,然後調製其之DMAc溶液(35重量%)。該溶液之調製係使用水平磨WILLY A.BACHOFEN公司製造之DYNO-MIL KDL,以填充85%之氧化鋯珠粒,且在50克/分鐘之流速的條件下,使各成份均勻溶解於DMAc。將此溶液作為添加劑溶液B6。(a) a compound, (b) a compound, and (c) a nitrogen-containing aromatic compound are each used in the addition polymer of (a2) divinylbenzene and p-cresol used in Example 2 (made by DuPont). Methacrol" (registered trademark) 2390), (a3) triethylene glycol-bis[3-(3-tris-butyl-5-methyl-4-hydroxyphenyl)propionate], and (a4) Ethyl-1,2-bis(3,3-bis[3-tris-butyl-4-hydroxyphenyl]butyrate), used in Example 1 (b1) with TBDEA and PICM 6 a repeater of up to 8 and reacting with UDMH to form a dimethyl half-carbocycle polymer at the end, and (b2) 4,4'-(methylene II) used in Example 4. -p-phenylene)bis(N,N-dimethylhalocyanine), and (c1)2,4-di(2',4'-dimethylphenyl)-6-(2"- Hydroxy-4"-alkoxyphenyl)-1,3,5-triazole And these were mixed at a ratio of 1.0:2.0:0.5:2.0:0.5:0.1, and then a DMAc solution (35 wt%) thereof was prepared. The solution was prepared by horizontally grinding DYNO-MIL KDL manufactured by WILLY A. BACHOFEN Co., Ltd. to fill 85% of zirconia beads, and the components were uniformly dissolved in DMAc at a flow rate of 50 g/min. This solution was used as the additive solution B6.
將在實施例3所調製之高分子溶液A2、如上所述之添加劑溶液B6分別以93.9重量%及6.1重量%之比率均勻混合,以作為紡絲溶液D6。The polymer solution A2 prepared in Example 3 and the additive solution B6 as described above were uniformly mixed at a ratio of 93.9 wt% and 6.1 wt%, respectively, to obtain a spinning solution D6.
將該紡絲溶液D6在設定導輥與捲取機之速度比為1.20、及以600公尺/分鐘之紡絲速度實施乾式紡絲並加以捲取,以製造22 dtex、2絲之複絲之聚胺基甲酸酯彈性紗(500克之紗線捲裝)。The spinning solution D6 was dry-spun at a speed ratio of 1.20 and a spinning speed of 600 m/min at a spinning speed of the set guide roller and the coiler to produce a 22 dtex, 2 filament multifilament. Polyurethane elastomer yarn (500 g yarn package).
用於構成所製得之聚胺基甲酸酯彈性紗的各成份之組成(重量%)係如表1所示,(a)化合物、(b)化合物及(c)含氮芳香族化合物係分別含有3.5重量%、2.5重量%及0.1重量%。The composition (% by weight) of each component constituting the obtained polyurethane elastic yarn is as shown in Table 1, (a) compound, (b) compound, and (c) nitrogen-containing aromatic compound system. It contained 3.5% by weight, 2.5% by weight, and 0.1% by weight, respectively.
從所製得之聚胺基甲酸酯彈性紗(22 dtex)與東麗工業股份有限公司製造之聚對苯二甲酸乙二醇酯長纖維(33 dtex、48絲)製造與實施例3之情形相同之兩路進線半平經編組織,以作為針織坯布(聚酯系伸縮性布帛)。就該針織坯布,實施在染色時之耐熱性3之試驗,評估在附著不飽和脂肪酸與重金屬時之染色時之耐熱性。此外,將其針織坯布加以染色後評估其外觀品質。Manufactured from the obtained polyurethane elastic yarn (22 dtex) and polyethylene terephthalate long fiber (33 dtex, 48 filament) manufactured by Toray Industries, Ltd. and Example 3 In the same situation, the two lines of the line are semi-finished and warp-knitted as a knitted fabric (polyester-based stretch fabric). With respect to the knitted fabric, a test for heat resistance 3 at the time of dyeing was carried out, and heat resistance at the time of dyeing with unsaturated fatty acid and heavy metal was evaluated. In addition, the knitted fabric was dyed and evaluated for its appearance quality.
並且,將就所製得之聚胺基甲酸酯彈性紗在反復進行染色時之耐熱性,以在染色時之耐熱性4之試驗加以評估。Further, the heat resistance of the obtained polyurethane elastic yarn upon repeated dyeing was evaluated by a test for heat resistance 4 at the time of dyeing.
該聚胺基甲酸酯彈性紗之斷裂伸度、斷裂強度、殘留變形率、應力鬆弛率、及熱定型性之指標的熱軟化點,係皆與未混合(b)化合物、(c)化合物之比較例2(如後所述)相同,且在加工性或坯布特性方面,並未觀察到經混合此等之添加劑所引起之不良影響。The thermal softening point of the elongation, fracture strength, residual deformation rate, stress relaxation rate, and heat setting property of the polyurethane elastic yarn is both unmixed (b) compound and (c) compound Comparative Example 2 (described later) was the same, and in terms of processability or fabric properties, no adverse effects caused by mixing such additives were observed.
此外,聚酯系伸縮性布帛在染色時之耐熱性,係在染色時之耐熱性3(對於不飽和脂肪酸與重金屬之耐性),連同在染色時之耐熱性4(對於反復進行染色之耐性),皆比比較例2顯現出大幅度地提高。並且,經加以染色所製得之伸縮性織物係無缺點,且具有優越的外觀品質者。In addition, the heat resistance of the polyester-based stretch fabric at the time of dyeing is heat resistance 3 at the time of dyeing (resistance to unsaturated fatty acids and heavy metals), together with heat resistance at the time of dyeing 4 (resistance to repeated dyeing) Both showed a significant improvement over Comparative Example 2. Further, the stretchable fabric obtained by dyeing is not disadvantageous and has superior appearance quality.
(a)化合物、(b)化合物及(c)含氮芳香族化合物係分別使用在實施例3使用之(a1)1,3,5-參(4-三級-丁基-3-羥基-2,6-二甲基苯甲基)-1,3,5-三氮-2,4,6(1H,3H,5H)-三酮、(a2)二乙烯基苯與對-甲酚之加成聚合物(杜邦公司製造之「Methacrol」(註冊商標)2390)、(b1)具有TBDEA與PICM之6至8之重覆數的加成物,且與UDMH進行反應以在末端形成二甲基半卡肼之聚合物、以及(c1)2,4-二(2’,4’-二甲基苯基)-6-(2”-羥基-4”-烷氧基苯基)-1,3,5-三氮,並將此等以1.0:1.0:3.0:005之比率混合,然後調製其之DMAc溶液( 35重量%)。該溶液之調製,係使用與實施例3相同之方法,亦即,使用水平磨WILLY A.BACHOFEN公司製造之DYNO-MIL KDL,以填充85%之氧化鋯珠粒,且在50克/分鐘之流速的條件下,使各成份均勻溶解於DMAc。將此溶液作為添加劑溶液B7。(a) a compound, (b) a compound, and (c) a nitrogen-containing aromatic compound are used in the (a1) 1,3,5-parameter (4-tris-butyl-3-hydroxy-) used in Example 3, respectively. 2,6-dimethylbenzyl)-1,3,5-triazole -2,4,6(1H,3H,5H)-trione, (a2) addition polymer of divinylbenzene and p-cresol (Methacrol (registered trademark) 2390, manufactured by DuPont), ( B1) an adduct having a repeat number of 6 to 8 of TBDEA and PICM, and reacting with UDMH to form a polymer of dimethylhalocyanine at the end, and (c1) 2,4-di (2' , 4'-dimethylphenyl)-6-(2"-hydroxy-4"-alkoxyphenyl)-1,3,5-triazole And these were mixed at a ratio of 1.0:1.0:3.0:005, and then a DMAc solution (35 wt%) thereof was prepared. The solution was prepared by the same method as in Example 3, that is, using DYNO-MIL KDL manufactured by WILLY A. BACHOFEN, Inc., to fill 85% of zirconia beads, and at 50 g/min. Under the conditions of the flow rate, the components were uniformly dissolved in DMAc. This solution was used as the additive solution B7.
將在實施例3所調製之高分子溶液A2、如上所述之添加劑溶液B7分別以94.95重量%及5.05重量%之比率均勻混合,以作為紡絲溶液D7。The polymer solution A2 prepared in Example 3 and the additive solution B7 as described above were uniformly mixed at a ratio of 94.95 wt% and 5.05 wt%, respectively, to obtain a spinning solution D7.
將該紡絲溶液D7在設定導輥與捲取機之速度比為1.20、及以600公尺/分鐘之紡絲速度實施乾式紡絲並加以捲取,以製造22 dtex、2絲之複絲之聚胺基甲酸酯彈性紗(500克之紗線捲裝)。The spinning solution D7 was dry-spun at a speed ratio of 1.20 at a set guide roller and a coiler, and was taken up at a spinning speed of 600 meters/minute to produce a 22 dtex, 2 filament multifilament. Polyurethane elastomer yarn (500 g yarn package).
用於構成所製得之聚胺基甲酸酯彈性紗的各成份之組成(重量%)係如表1所示,(a)化合物、(b)化合物及(c)含氮芳香族化合物係分別含有2.0重量%、3.0重量%及0.05重量%。The composition (% by weight) of each component constituting the obtained polyurethane elastic yarn is as shown in Table 1, (a) compound, (b) compound, and (c) nitrogen-containing aromatic compound system. It is contained in an amount of 2.0% by weight, 3.0% by weight, and 0.05% by weight, respectively.
從所製得之聚胺基甲酸酯彈性紗(22 dtex)與東麗工業股份有限公司製造之聚對苯二甲酸乙二醇酯長纖維(33 dtex、48絲)製造與實施例3之情形相同之兩路進線半平經編組織,以作為針織坯布(聚酯系伸縮性布帛)。就該針織坯布,實施在染色時之耐熱性3之試驗,評估在附著不飽和脂肪酸與重金屬時之染色時之耐熱性。此外,將其針織坯布加以染色後評估其外觀品質。Manufactured from the obtained polyurethane elastic yarn (22 dtex) and polyethylene terephthalate long fiber (33 dtex, 48 filament) manufactured by Toray Industries, Ltd. and Example 3 In the same situation, the two lines of the line are semi-finished and warp-knitted as a knitted fabric (polyester-based stretch fabric). With respect to the knitted fabric, a test for heat resistance 3 at the time of dyeing was carried out, and heat resistance at the time of dyeing with unsaturated fatty acid and heavy metal was evaluated. In addition, the knitted fabric was dyed and evaluated for its appearance quality.
並且,將就所製得之聚胺基甲酸酯彈性紗在反復進行 染色時之耐熱性,以在染色時之耐熱性4之試驗加以評估。And, the polyurethane elastic yarn obtained will be repeated The heat resistance at the time of dyeing was evaluated by the test of heat resistance 4 at the time of dyeing.
該聚胺基甲酸酯彈性紗之斷裂伸度、斷裂強度、殘留變形率、應力鬆弛率、及熱定型性之指標的熱軟化點,係皆與未混合(b)化合物、(c)化合物之比較例2(如後所述)相同,且在加工性或坯布特性方面,並未觀察到經混合此等之添加劑所引起之不良影響。The thermal softening point of the elongation, fracture strength, residual deformation rate, stress relaxation rate, and heat setting property of the polyurethane elastic yarn is both unmixed (b) compound and (c) compound Comparative Example 2 (described later) was the same, and in terms of processability or fabric properties, no adverse effects caused by mixing such additives were observed.
此外,聚酯系伸縮性布帛在染色時之耐熱性,係在染色時之耐熱性3(對於不飽和脂肪酸與重金屬之耐性),連同在染色時之耐熱性4(對於反復進行染色之耐性),皆比比較例2顯現出大幅度地提高。但是,耐熱性4,若與(c)含氮芳香族化合物以外之所有添加劑之種類、添加量為相同,而僅為c1之添加量為不同的實施例3比較時,卻為稍差者。並且,經加以染色所製得之伸縮性織物係無缺點,且具有優越的外觀品質者。In addition, the heat resistance of the polyester-based stretch fabric at the time of dyeing is heat resistance 3 at the time of dyeing (resistance to unsaturated fatty acids and heavy metals), together with heat resistance at the time of dyeing 4 (resistance to repeated dyeing) Both showed a significant improvement over Comparative Example 2. However, the heat resistance 4 is slightly worse when the types and addition amounts of all the additives other than the (c) nitrogen-containing aromatic compound are the same, and only the amount of addition of c1 is different. Further, the stretchable fabric obtained by dyeing is not disadvantageous and has superior appearance quality.
(a)化合物、(b)化合物及(c)含氮芳香族化合物係分別使用在實施例3使用之(a1)1,3,5-參(4-三級-丁基-3-羥基-2,6-二甲基苯甲基)-1,3,5-三氮-2,4,6(1H,3H,5H)-三酮、(a2)二乙烯基苯與對-甲酚之加成聚合物(杜邦公司製造之「Methacrol」(註冊商標)2390)、(b1)具有TBDEA與PICM之6至8之重覆數的加成物,且與UDMH進行反應以在末端形成二甲基半卡肼之聚合物、以及(c1)2,4-二(2’,4’-二甲基苯基)-6-(2”-羥基- 4”-烷氧基苯基)-1,3,5-三氮,並將此等以1.0:1.0:3.0:0.15之比率混合,然後調製其之DMAc溶液(35重量%)。該溶液之調製,係使用與實施例3相同之方法,亦即,使用水平磨WILLY A.BACHOFEN公司製造之DYNO-MIL KDL,以填充85%之氧化鋯珠粒,且在50克/分鐘之流速的條件下,使各成份均勻溶解於DMAc。將此溶液作為添加劑溶液B8。(a) a compound, (b) a compound, and (c) a nitrogen-containing aromatic compound are used in the (a1) 1,3,5-parameter (4-tris-butyl-3-hydroxy-) used in Example 3, respectively. 2,6-dimethylbenzyl)-1,3,5-triazole -2,4,6(1H,3H,5H)-trione, (a2) addition polymer of divinylbenzene and p-cresol (Methacrol (registered trademark) 2390, manufactured by DuPont), ( B1) an adduct having a repeat number of 6 to 8 of TBDEA and PICM, and reacting with UDMH to form a polymer of dimethylhalocyanine at the end, and (c1) 2,4-di (2' , 4'-dimethylphenyl)-6-(2"-hydroxy-4"-alkoxyphenyl)-1,3,5-triazole And these were mixed at a ratio of 1.0:1.0:3.0:0.15, and then a DMAc solution (35 wt%) thereof was prepared. The solution was prepared by the same method as in Example 3, that is, using DYNO-MIL KDL manufactured by WILLY A. BACHOFEN, Inc., to fill 85% of zirconia beads, and at 50 g/min. Under the conditions of the flow rate, the components were uniformly dissolved in DMAc. This solution was used as the additive solution B8.
將在實施例3所調製之高分子溶液A2、如上所述之添加劑溶液B8分別以94.85重量%及5.15重量%之比率均勻混合,以作為紡絲溶液D8。The polymer solution A2 prepared in Example 3 and the additive solution B8 as described above were uniformly mixed at a ratio of 94.85% by weight and 5.15% by weight, respectively, to obtain a spinning solution D8.
將該紡絲溶液D8在設定導輥與捲取機之速度比為1.20、及以600公尺/分鐘之紡絲速度實施乾式紡絲並加以捲取,以製造22 dtex、2絲之複絲之聚胺基甲酸酯彈性紗(500克之紗線捲裝)。The spinning solution D8 was dry-spun and coiled at a speed ratio of 1.20 and a spinning speed of 600 m/min to produce a 22 dtex, 2 filament multifilament. Polyurethane elastomer yarn (500 g yarn package).
用於構成所製得之聚胺基甲酸酯彈性紗的各成份之組成(重量%)係如表3所示,(a)化合物、(b)化合物及(c)含氮芳香族化合物係分別含有2.0重量%、3.0重量%及0.15重量%。The composition (% by weight) of each component constituting the obtained polyurethane elastic yarn is shown in Table 3, (a) compound, (b) compound, and (c) nitrogen-containing aromatic compound system. It is contained in an amount of 2.0% by weight, 3.0% by weight, and 0.15% by weight, respectively.
從所製得之聚胺基甲酸酯彈性紗(22 dtex)與東麗工業股份有限公司製造之聚對苯二甲酸乙二醇酯長纖維(33 dtex、48絲)製造與實施例3之情形相同之兩路進線半平經編組織,以作為針織坯布(聚酯系伸縮性布帛)。就該針織坯布,實施在染色時之耐熱性3之試驗,評估在附著不飽和脂肪酸與重金屬時之染色時之耐熱性。此外,將其 針織坯布加以染色後評估其外觀品質。Manufactured from the obtained polyurethane elastic yarn (22 dtex) and polyethylene terephthalate long fiber (33 dtex, 48 filament) manufactured by Toray Industries, Ltd. and Example 3 In the same situation, the two lines of the line are semi-finished and warp-knitted as a knitted fabric (polyester-based stretch fabric). With respect to the knitted fabric, a test for heat resistance 3 at the time of dyeing was carried out, and heat resistance at the time of dyeing with unsaturated fatty acid and heavy metal was evaluated. In addition, it will The knitted fabric was dyed and evaluated for its appearance quality.
並且,將就所製得之聚胺基甲酸酯彈性紗在反復進行染色時之耐熱性,以在染色時之耐熱性4之試驗加以評估。Further, the heat resistance of the obtained polyurethane elastic yarn upon repeated dyeing was evaluated by a test for heat resistance 4 at the time of dyeing.
該聚胺基甲酸酯彈性紗之斷裂伸度、斷裂強度、殘留變形率、應力鬆弛率、及熱定型性之指標的熱軟化點,係皆與未混合(b)化合物、(c)化合物之比較例2(如後所述)相同,且在加工性或坯布特性方面,並未觀察到經混合此等之添加劑所引起之不良影響。The thermal softening point of the elongation, fracture strength, residual deformation rate, stress relaxation rate, and heat setting property of the polyurethane elastic yarn is both unmixed (b) compound and (c) compound Comparative Example 2 (described later) was the same, and in terms of processability or fabric properties, no adverse effects caused by mixing such additives were observed.
此外,聚酯系伸縮性布帛在染色時之耐熱性,係在染色時之耐熱性3(對於不飽和脂肪酸與重金屬之耐性),連同在染色時之耐熱性4(對於反復進行染色之耐性),皆比比較例2顯現出大幅度地提高。並且,經加以染色所製得之伸縮性織物係無缺點,且具有優越的外觀品質者。In addition, the heat resistance of the polyester-based stretch fabric at the time of dyeing is heat resistance 3 at the time of dyeing (resistance to unsaturated fatty acids and heavy metals), together with heat resistance at the time of dyeing 4 (resistance to repeated dyeing) Both showed a significant improvement over Comparative Example 2. Further, the stretchable fabric obtained by dyeing is not disadvantageous and has superior appearance quality.
(a)化合物、(b)化合物及(c)含氮芳香族化合物係分別使用在實施例3使用之(a1)1,3,5-參(4-三級-丁基-3-羥基-2,6-二甲基苯甲基)-1,3,5-三氮-2,4,6(1H,3H,5H)-三酮、(a2)二乙烯基苯與對-甲酚之加成聚合物(杜邦公司製造之「Methacrol」(註冊商標)2390)、(b1)具有TBDEA與PICM之6至8之重覆數的加成物,且與UDMH進行反應以在末端形成二甲基半卡肼之聚合物、以及(c1)2,4-二(2’,4’-二甲基苯基)-6-(2”-羥基-4”-烷氧基苯基)-1,3,5-三氮,並將此等以 1.0:1.0:3.0:0.20之比率混合,然後調製其之DMAc溶液(35重量%)。該溶液之調製,係使用與實施例3相同之方法,亦即,使用水平磨WILLY A.BACHOFEN公司製造之DYNO-MIL KDL,以填充85%之氧化鋯珠粒,且在50克/分鐘之流速的條件下,使各成份均勻溶解於DMAc。將此溶液作為添加劑溶液B9。(a) a compound, (b) a compound, and (c) a nitrogen-containing aromatic compound are used in the (a1) 1,3,5-parameter (4-tris-butyl-3-hydroxy-) used in Example 3, respectively. 2,6-dimethylbenzyl)-1,3,5-triazole -2,4,6(1H,3H,5H)-trione, (a2) addition polymer of divinylbenzene and p-cresol (Methacrol (registered trademark) 2390, manufactured by DuPont), ( B1) an adduct having a repeat number of 6 to 8 of TBDEA and PICM, and reacting with UDMH to form a polymer of dimethylhalocyanine at the end, and (c1) 2,4-di (2' , 4'-dimethylphenyl)-6-(2"-hydroxy-4"-alkoxyphenyl)-1,3,5-triazole And these were mixed at a ratio of 1.0:1.0:3.0:0.20, and then a DMAc solution (35 wt%) thereof was prepared. The solution was prepared by the same method as in Example 3, that is, using DYNO-MIL KDL manufactured by WILLY A. BACHOFEN, Inc., to fill 85% of zirconia beads, and at 50 g/min. Under the conditions of the flow rate, the components were uniformly dissolved in DMAc. This solution was used as the additive solution B9.
將在實施例3所調製之高分子溶液A2、如上所述之添加劑溶液B9分別以94.80重量%及5.20重量%之比率均勻混合,以作為紡絲溶液D9。The polymer solution A2 prepared in Example 3 and the additive solution B9 as described above were uniformly mixed at a ratio of 94.80% by weight and 5.20% by weight, respectively, to obtain a spinning solution D9.
將該紡絲溶液D9在設定導輥與捲取機之速度比為1.20、及以600公尺/分鐘之紡絲速度實施乾式紡絲並加以捲取,以製造22 dtex、2絲之複絲之聚胺基甲酸酯彈性紗(500克之紗線捲裝)。The spinning solution D9 was dry-spun at a speed ratio of 1.20 and a spinning speed of 600 m/min at a spinning speed of the set guide roller and the coiler to produce a 22 dtex, 2 filament multifilament. Polyurethane elastomer yarn (500 g yarn package).
用於構成所製得之聚胺基甲酸酯彈性紗的各成份之組成(重量%)係如表3所示,(a)化合物、(b)化合物及(c)含氮芳香族化合物係分別含有2.0重量%、3.0重量%及0.20重量%。The composition (% by weight) of each component constituting the obtained polyurethane elastic yarn is shown in Table 3, (a) compound, (b) compound, and (c) nitrogen-containing aromatic compound system. It is contained in an amount of 2.0% by weight, 3.0% by weight, and 0.20% by weight, respectively.
從所製得之聚胺基甲酸酯彈性紗(22 dtex)與東麗工業股份有限公司製造之聚對苯二甲酸乙二醇酯長纖維(33 dtex、48絲)製造與實施例3之情形相同之兩路進線半平經編組織,以作為針織坯布(聚酯系伸縮性布帛)。就該針織坯布,實施在染色時之耐熱性3之試驗,評估在附著不飽和脂肪酸與重金屬時之染色時之耐熱性。此外,將其針織坯布加以染色後評估其外觀品質。Manufactured from the obtained polyurethane elastic yarn (22 dtex) and polyethylene terephthalate long fiber (33 dtex, 48 filament) manufactured by Toray Industries, Ltd. and Example 3 In the same situation, the two lines of the line are semi-finished and warp-knitted as a knitted fabric (polyester-based stretch fabric). With respect to the knitted fabric, a test for heat resistance 3 at the time of dyeing was carried out, and heat resistance at the time of dyeing with unsaturated fatty acid and heavy metal was evaluated. In addition, the knitted fabric was dyed and evaluated for its appearance quality.
並且,將就所製得之聚胺基甲酸酯彈性紗在反復進行染色時之耐熱性,以在染色時之耐熱性4之試驗加以評估。Further, the heat resistance of the obtained polyurethane elastic yarn upon repeated dyeing was evaluated by a test for heat resistance 4 at the time of dyeing.
該聚胺基甲酸酯彈性紗之斷裂伸度、斷裂強度、殘留變形率、應力鬆弛率、及熱定型性之指標的熱軟化點,係皆與未混合(b)化合物、(c)化合物之比較例2(如後所述)相同,且在加工性或坯布特性方面,並未觀察到經混合此等之添加劑所引起之不良影響。The thermal softening point of the elongation, fracture strength, residual deformation rate, stress relaxation rate, and heat setting property of the polyurethane elastic yarn is both unmixed (b) compound and (c) compound Comparative Example 2 (described later) was the same, and in terms of processability or fabric properties, no adverse effects caused by mixing such additives were observed.
此外,聚酯系伸縮性布帛在染色時之耐熱性,係在染色時之耐熱性3(對於不飽和脂肪酸與重金屬之耐性),連同在染色時之耐熱性4(對於反復進行染色之耐性),皆比比較例2顯現出大幅度地提高。但是,耐熱性3、耐熱性4,若與(c)含氮芳香族化合物以外之所有之添加劑的種類、添加量為相同而僅為c1之添加量不同之實施例3相比較時,卻為稍差者。並且,經加以染色所製得之伸縮性織物係無缺點,且具有優越的外觀品質者。In addition, the heat resistance of the polyester-based stretch fabric at the time of dyeing is heat resistance 3 at the time of dyeing (resistance to unsaturated fatty acids and heavy metals), together with heat resistance at the time of dyeing 4 (resistance to repeated dyeing) Both showed a significant improvement over Comparative Example 2. However, when heat resistance 3 and heat resistance 4 are compared with Example 3 in which the types and addition amounts of all the additives other than the (c) nitrogen-containing aromatic compound are the same, and only the addition amount of c1 is different, A little worse. Further, the stretchable fabric obtained by dyeing is not disadvantageous and has superior appearance quality.
(a)化合物、(b)化合物及(c)含氮芳香族化合物係分別使用在實施例3使用之(a1)1,3,5-參(4-三級-丁基-3-羥基-2,6-二甲基苯甲基)-1,3,5-三氮-2,4,6(1H,3H,5H)-三酮、(a2)二乙烯基苯與對-甲酚之加成聚合物(杜邦公司製造之「Methacrol」(註冊商標)2390)、(b1)具有TBDEA與PICM之6至8之重覆數的加成物,且與UDMH進行反應以在末端形成二甲基半卡肼之聚合 物、以及(c1)2,4-二(2’,4’-二甲基苯基)-6-(2”-羥基-4”-烷氧基苯基)-1,3,5-三氮,並將此等以1.0:1.0:3.0:0.25之比率混合,然後調製其之DMAc溶液(35重量%)。該溶液之調製,係使用與實施例3相同之方法,亦即,使用水平磨WILLY A.BACHOFEN公司製造之DYNO-MIL KDL,以填充85%之氧化鋯珠粒,且在50克/分鐘之流速的條件下,使各成份均勻溶解於DMAc。將此溶液作為添加劑溶液B10。(a) a compound, (b) a compound, and (c) a nitrogen-containing aromatic compound are used in the (a1) 1,3,5-parameter (4-tris-butyl-3-hydroxy-) used in Example 3, respectively. 2,6-dimethylbenzyl)-1,3,5-triazole -2,4,6(1H,3H,5H)-trione, (a2) addition polymer of divinylbenzene and p-cresol (Methacrol (registered trademark) 2390, manufactured by DuPont), ( B1) an adduct having a repeat number of 6 to 8 of TBDEA and PICM, and reacting with UDMH to form a polymer of dimethylhalocyanine at the end, and (c1) 2,4-di (2' , 4'-dimethylphenyl)-6-(2"-hydroxy-4"-alkoxyphenyl)-1,3,5-triazole And these were mixed at a ratio of 1.0:1.0:3.0:0.25, and then a DMAc solution (35 wt%) thereof was prepared. The solution was prepared by the same method as in Example 3, that is, using DYNO-MIL KDL manufactured by WILLY A. BACHOFEN, Inc., to fill 85% of zirconia beads, and at 50 g/min. Under the conditions of the flow rate, the components were uniformly dissolved in DMAc. This solution was used as the additive solution B10.
將在實施例3所調製之高分子溶液A2、如上所述之添加劑溶液B10分別以94.75重量%及5.25重量%之比率均勻混合,以作為紡絲溶液D10。The polymer solution A2 prepared in Example 3 and the additive solution B10 as described above were uniformly mixed at a ratio of 94.75 wt% and 5.25 wt%, respectively, to obtain a spinning solution D10.
將該紡絲溶液D10在設定導輥與捲取機之速度比為1.20、及以600公尺/分鐘之紡絲速度實施乾式紡絲並加以捲取,以製造22 dtex、2絲之複絲之聚胺基甲酸酯彈性紗(500克之紗線捲裝)。The spinning solution D10 was dry-spun at a speed ratio of 1.20 and a spinning speed of 600 m/min to produce a 22 dtex, 2 filament multifilament. Polyurethane elastomer yarn (500 g yarn package).
用於構成所製得之聚胺基甲酸酯彈性紗的各成份之組成(重量%)係如表3所示,(a)化合物、(b)化合物及(c)含氮芳香族化合物係分別含有2.0重量%、3.0重量%及0.25重量%。The composition (% by weight) of each component constituting the obtained polyurethane elastic yarn is shown in Table 3, (a) compound, (b) compound, and (c) nitrogen-containing aromatic compound system. It is contained in an amount of 2.0% by weight, 3.0% by weight, and 0.25% by weight, respectively.
從所製得之聚胺基甲酸酯彈性紗(22 dtex)與東麗工業股份有限公司製造之聚對苯二甲酸乙二醇酯長纖維(33 dtex、48絲)製造與實施例3之情形相同之兩路進線半平經編組織,以作為針織坯布(聚酯系伸縮性布帛)。就該針織坯布,實施在染色時之耐熱性3之試驗,評估在附著 不飽和脂肪酸與重金屬時之染色時之耐熱性。此外,將其針織坯布加以染色後評估其外觀品質。Manufactured from the obtained polyurethane elastic yarn (22 dtex) and polyethylene terephthalate long fiber (33 dtex, 48 filament) manufactured by Toray Industries, Ltd. and Example 3 In the same situation, the two lines of the line are semi-finished and warp-knitted as a knitted fabric (polyester-based stretch fabric). In the case of the knitted fabric, the heat resistance 3 at the time of dyeing was carried out, and the evaluation was attached. Heat resistance when dyed with unsaturated fatty acids and heavy metals. In addition, the knitted fabric was dyed and evaluated for its appearance quality.
並且,將就所製得之聚胺基甲酸酯彈性紗在反復進行染色時之耐熱性,以在染色時之耐熱性4之試驗加以評估。Further, the heat resistance of the obtained polyurethane elastic yarn upon repeated dyeing was evaluated by a test for heat resistance 4 at the time of dyeing.
該聚胺基甲酸酯彈性紗之斷裂伸度、斷裂強度、殘留變形率、應力鬆弛率、及熱定型性之指標的熱軟化點,係皆與未混合(b)化合物、(c)化合物之比較例2(如後所述)相同,且在加工性或坯布特性方面,並未觀察到經混合此等之添加劑所引起之不良影響。The thermal softening point of the elongation, fracture strength, residual deformation rate, stress relaxation rate, and heat setting property of the polyurethane elastic yarn is both unmixed (b) compound and (c) compound Comparative Example 2 (described later) was the same, and in terms of processability or fabric properties, no adverse effects caused by mixing such additives were observed.
此外,聚酯系伸縮性布帛在染色時之耐熱性,係在染色時之耐熱性3(對於不飽和脂肪酸與重金屬之耐性),連同在染色時之耐熱性4(對於反復進行染色之耐性),皆比比較例2顯現出大幅度地提高。但是,耐熱性3、耐熱性4,若與(c)含氮芳香族化合物以外之所有添加劑之種類、添加量為相同、而僅為c1之添加量為不同的實施例3相比較時,卻為稍差者。並且,經加以染色所製得之伸縮性織物係無缺點,且具有優越的外觀品質者。In addition, the heat resistance of the polyester-based stretch fabric at the time of dyeing is heat resistance 3 at the time of dyeing (resistance to unsaturated fatty acids and heavy metals), together with heat resistance at the time of dyeing 4 (resistance to repeated dyeing) Both showed a significant improvement over Comparative Example 2. However, when heat resistance 3 and heat resistance 4 are the same as those of (c) the nitrogen-containing aromatic compound, the types and addition amounts of all the additives are the same, and only the addition amount of c1 is different, For the worse. Further, the stretchable fabric obtained by dyeing is not disadvantageous and has superior appearance quality.
(a)化合物、(b)化合物及(c)含氮芳香族化合物係分別使用在實施例3使用之(a1)1,3,5-參(4-三級-丁基-3-羥基-2,6-二甲基苯甲基)-1,3,5-三氮-2,4,6(1H,3H,5H)-三酮、(a2)二乙烯基苯與對-甲酚之加成聚合物(杜邦公司製造之「Methacrol」(註冊商標)2390) 、(b1)具有TBDEA與PICM之6至8之重覆數的加成物,且與UDMH進行反應以在末端形成二甲基半卡肼之聚合物、以及(c1)2,4-二(2’,4’-二甲基苯基)-6-(2”-羥基-4”-烷氧基苯基)-1,3,5-三氮,並將此等以1.0:10:3.0:0.30之比率混合,然後調製其之DMAc溶液(35重量%)。該溶液之調製,係使用與實施例3相同之方法,亦即,使用水平磨WILLY A.BACHOFEN公司製造之DYNO-MIL KDL,以填充85%之氧化鋯珠粒,且在50克/分鐘之流速的條件下,使各成份均勻溶解於DMAc。將此溶液作為添加劑溶液B11。(a) a compound, (b) a compound, and (c) a nitrogen-containing aromatic compound are used in the (a1) 1,3,5-parameter (4-tris-butyl-3-hydroxy-) used in Example 3, respectively. 2,6-dimethylbenzyl)-1,3,5-triazole -2,4,6(1H,3H,5H)-trione, (a2) addition polymer of divinylbenzene and p-cresol (Methacrol (registered trademark) 2390 by DuPont), ( B1) an adduct having a repeat number of 6 to 8 of TBDEA and PICM, and reacting with UDMH to form a polymer of dimethylhalocyanine at the end, and (c1) 2,4-di (2' , 4'-dimethylphenyl)-6-(2"-hydroxy-4"-alkoxyphenyl)-1,3,5-triazole And these were mixed at a ratio of 1.0:10:3.0:0.30, and then a DMAc solution (35 wt%) thereof was prepared. The solution was prepared by the same method as in Example 3, that is, using DYNO-MIL KDL manufactured by WILLY A. BACHOFEN, Inc., to fill 85% of zirconia beads, and at 50 g/min. Under the conditions of the flow rate, the components were uniformly dissolved in DMAc. This solution was used as the additive solution B11.
將在實施例3所調製之高分子溶液A2、如上所述之添加劑溶液B11分別以94.70重量%及5.30重量%之比率均勻混合,以作為紡絲溶液D11。The polymer solution A2 prepared in Example 3 and the additive solution B11 as described above were uniformly mixed at a ratio of 94.70% by weight and 5.30% by weight, respectively, to obtain a spinning solution D11.
將該紡絲溶液D11在設定導輥與捲取機之速度比為1.20、及以600公尺/分鐘之紡絲速度實施乾式紡絲並加以捲取,以製造22 dtex、2絲之複絲之聚胺基甲酸酯彈性紗(500克之紗線捲裝)。The spinning solution D11 was dry-spun at a speed ratio of 1.20 and a spinning speed of 600 m/min, and was wound up to produce a 22 dtex, 2 filament multifilament. Polyurethane elastomer yarn (500 g yarn package).
用於構成所製得之聚胺基甲酸酯彈性紗的各成份之組成(重量%)係如表3所示,(a)化合物、(b)化合物及(c)含氮芳香族化合物係分別含有2.0重量%、3.0重量%及0.30重量%。The composition (% by weight) of each component constituting the obtained polyurethane elastic yarn is shown in Table 3, (a) compound, (b) compound, and (c) nitrogen-containing aromatic compound system. It is contained in an amount of 2.0% by weight, 3.0% by weight, and 0.30% by weight, respectively.
從所製得之聚胺基甲酸酯彈性紗(22 dtex)與東麗工業股份有限公司製造之聚對苯二甲酸乙二醇酯長纖維(33 dtex、48絲)製造與實施例3之情形相同之兩路進線半平 經編組織,以作為針織坯布(聚酯系伸縮性布帛)。就該針織坯布,實施在染色時之耐熱性3之試驗,評估在附著不飽和脂肪酸與重金屬時之染色時之耐熱性。此外,將其針織坯布加以染色後評估其外觀品質。Manufactured from the obtained polyurethane elastic yarn (22 dtex) and polyethylene terephthalate long fiber (33 dtex, 48 filament) manufactured by Toray Industries, Ltd. and Example 3 The same situation, the two lines are half-flat Warp knitted tissue as a knitted fabric (polyester-based stretch fabric). With respect to the knitted fabric, a test for heat resistance 3 at the time of dyeing was carried out, and heat resistance at the time of dyeing with unsaturated fatty acid and heavy metal was evaluated. In addition, the knitted fabric was dyed and evaluated for its appearance quality.
並且,將就所製得之聚胺基甲酸酯彈性紗在反復進行染色時之耐熱性,以在染色時之耐熱性4之試驗加以評估。Further, the heat resistance of the obtained polyurethane elastic yarn upon repeated dyeing was evaluated by a test for heat resistance 4 at the time of dyeing.
該聚胺基甲酸酯彈性紗之斷裂伸度、斷裂強度、殘留變形率、應力鬆弛率、及熱定型性之指標的熱軟化點,係皆與未混合(b)化合物、(c)化合物之比較例2(如後所述)相同,且在加工性或坯布特性方面,並未觀察到經混合此等之添加劑所引起之不良影響。The thermal softening point of the elongation, fracture strength, residual deformation rate, stress relaxation rate, and heat setting property of the polyurethane elastic yarn is both unmixed (b) compound and (c) compound Comparative Example 2 (described later) was the same, and in terms of processability or fabric properties, no adverse effects caused by mixing such additives were observed.
此外,聚酯系伸縮性布帛在染色時之耐熱性,係在染色時之耐熱性3(對於不飽和脂肪酸與重金屬之耐性),連同在染色時之耐熱性4(對於反復進行染色之耐性),皆比比較例2顯現出大幅度地提高。並且,經加以染色所製得之伸縮性織物係無缺點,且具有優越的外觀品質者。In addition, the heat resistance of the polyester-based stretch fabric at the time of dyeing is heat resistance 3 at the time of dyeing (resistance to unsaturated fatty acids and heavy metals), together with heat resistance at the time of dyeing 4 (resistance to repeated dyeing) Both showed a significant improvement over Comparative Example 2. Further, the stretchable fabric obtained by dyeing is not disadvantageous and has superior appearance quality.
(a)化合物、(b)化合物及(c)含氮芳香族化合物係分別使用在實施例4使用之(a3)三甘醇-雙〔3-(3-三級-丁基-5-甲基-4-羥基苯基)丙酸酯〕、在實施例3使用之(b1)具有TBDEA與PICM之6至8之重覆數的加成物,且與UDMH進行反應以在末端形成二甲基半卡肼之聚合物、以及(c1)2,4-二(2’,4’-二甲基苯基)-6-(2”-羥基- 4”-烷氧基苯基)-1,3,5-三氮,並將此等以2.0:3.0:0.1之比率混合,然後調製其之DMAc溶液(35重量%)。該溶液之調製係使用水平磨WILLY A.BACHOFEN公司製造之DYNO-MIL KDL,以填充85%之氧化鋯珠粒,且在50克/分鐘之流速的條件下,使各成份均勻溶解於DMAc。將此溶液作為添加劑溶液B12。(a) a compound, (b) a compound, and (c) a nitrogen-containing aromatic compound are used in the (a3) triethylene glycol-bis[3-(3-tris-butyl-5-A) used in Example 4, respectively. (4-hydroxyphenyl)propionate], (b1) an adduct having a repeat number of 6 to 8 of TBDEA and PICM used in Example 3, and reacting with UDMH to form a dimethyl group at the terminal a polymer of a half-calendar, and (c1) 2,4-bis(2',4'-dimethylphenyl)-6-(2"-hydroxy- 4"-alkoxyphenyl)-1,3,5-trinitrogen, and these were mixed at a ratio of 2.0:3.0:0.1, and then a DMAc solution (35 wt%) thereof was prepared. DYNO-MIL KDL manufactured by WILLY A. BACHOFEN was used to fill 85% of zirconia beads, and the components were uniformly dissolved in DMAc at a flow rate of 50 g/min. Solution B12.
將在實施例3所調製之高分子溶液A2、如上所述之添加劑溶液B12分別以94.9重量%及5.1重量%之比率均勻混合,以作為紡絲溶液D12。The polymer solution A2 prepared in Example 3 and the additive solution B12 as described above were uniformly mixed at a ratio of 94.9 wt% and 5.1 wt%, respectively, to obtain a spinning solution D12.
將該紡絲溶液D12在設定導輥與捲取機之速度比為1.20、及以600公尺/分鐘之紡絲速度實施乾式紡絲並加以捲取,以製造22 dtex、2絲之複絲之聚胺基甲酸酯彈性紗(500克之紗線捲裝)。The spinning solution D12 was dry-spun at a speed ratio of 1.20 and a spinning speed of 600 m/min at a spinning speed of the set guide roller and the coiler to produce a 22 dtex, 2 filament multifilament. Polyurethane elastomer yarn (500 g yarn package).
用於構成所製得之聚胺基甲酸酯彈性紗的各成份之組成(重量%)係如表3所示,(a)化合物、(b)化合物及(c)含氮芳香族化合物係分別含有2.0重量%、3.0重量%及0.1重量%。The composition (% by weight) of each component constituting the obtained polyurethane elastic yarn is shown in Table 3, (a) compound, (b) compound, and (c) nitrogen-containing aromatic compound system. It is contained in an amount of 2.0% by weight, 3.0% by weight, and 0.1% by weight, respectively.
從所製得之聚胺基甲酸酯彈性紗(22 dtex)與東麗工業股份有限公司製造之聚對苯二甲酸乙二醇酯長纖維(33 dtex、48絲)製造與實施例3之情形相同之兩路進線半平經編組織,以作為針織坯布(聚酯系伸縮性布帛)。就該針織坯布,實施在染色時之耐熱性3之試驗,評估在附著不飽和脂肪酸與重金屬時之染色時之耐熱性。此外,將其針織坯布加以染色後評估其外觀品質。Manufactured from the obtained polyurethane elastic yarn (22 dtex) and polyethylene terephthalate long fiber (33 dtex, 48 filament) manufactured by Toray Industries, Ltd. and Example 3 In the same situation, the two lines of the line are semi-finished and warp-knitted as a knitted fabric (polyester-based stretch fabric). With respect to the knitted fabric, a test for heat resistance 3 at the time of dyeing was carried out, and heat resistance at the time of dyeing with unsaturated fatty acid and heavy metal was evaluated. In addition, the knitted fabric was dyed and evaluated for its appearance quality.
並且,將就所製得之聚胺基甲酸酯彈性紗在反復進行染色時之耐熱性,以在染色時之耐熱性4之試驗加以評估。Further, the heat resistance of the obtained polyurethane elastic yarn upon repeated dyeing was evaluated by a test for heat resistance 4 at the time of dyeing.
該聚胺基甲酸酯彈性紗之斷裂伸度、斷裂強度、殘留變形率、應力鬆弛率、及熱定型性之指標的熱軟化點,係皆與未混合(b)化合物、(c)化合物之比較例2(如後所述)相同,且在加工性或坯布特性方面,並未觀察到經混合此等之添加劑所引起之不良影響。The thermal softening point of the elongation, fracture strength, residual deformation rate, stress relaxation rate, and heat setting property of the polyurethane elastic yarn is both unmixed (b) compound and (c) compound Comparative Example 2 (described later) was the same, and in terms of processability or fabric properties, no adverse effects caused by mixing such additives were observed.
此外,聚酯系伸縮性布帛在染色時之耐熱性,係在染色時之耐熱性3(對於不飽和脂肪酸與重金屬之耐性),連同在染色時之耐熱性4(對於反復進行染色之耐性),皆比比較例2顯現出大幅度地提高。並且,經加以染色所製得之伸縮性織物係無缺點,且具有優越的外觀品質者。In addition, the heat resistance of the polyester-based stretch fabric at the time of dyeing is heat resistance 3 at the time of dyeing (resistance to unsaturated fatty acids and heavy metals), together with heat resistance at the time of dyeing 4 (resistance to repeated dyeing) Both showed a significant improvement over Comparative Example 2. Further, the stretchable fabric obtained by dyeing is not disadvantageous and has superior appearance quality.
(a)化合物、(b)化合物及(c)含氮芳香族化合物係分別使用在實施例5使用之(a4)伸乙基-1,2-雙(3,3-雙〔3-三級-丁基-4-羥基苯基〕丁酸酯)、在實施例3使用之(b1)具有TBDEA與PICM之6至8之重覆數的加成物,且與UDMH進行反應以在末端形成二甲基半卡肼之聚合物、以及(c1)2,4-二(2’,4’-二甲基苯基)-6-(2”-羥基-4”-烷氧基苯基)-1,3,5-三氮,並將此等以2.0:3.0:0.1之比率混合,然後調製其之DMAc溶液(35重量%)。該溶液之調製係使用水平磨WILLY A.BACHOFEN公司製造之DYNO-MIL KDL,以填充85%之氧 化鋯珠粒,且在50克/分鐘之流速的條件下,使各成份均勻溶解於DMAc。將此溶液作為添加劑溶液B13。(a) a compound, (b) a compound, and (c) a nitrogen-containing aromatic compound are respectively used in the embodiment (a4) exoethyl-1,2-bis(3,3-bis[3-tride] -butyl-4-hydroxyphenyl]butyrate), (b1) an adduct having a repeat number of 6 to 8 of TBDEA and PICM used in Example 3, and reacted with UDMH to form at the end a polymer of dimethylhalocyanine and (c1) 2,4-bis(2',4'-dimethylphenyl)-6-(2"-hydroxy-4"-alkoxyphenyl) -1,3,5-trinitrogen And these were mixed at a ratio of 2.0:3.0:0.1, and then a DMAc solution (35 wt%) thereof was prepared. The solution was prepared by horizontally grinding DYNO-MIL KDL manufactured by WILLY A. BACHOFEN Co., Ltd. to fill 85% of zirconia beads, and the components were uniformly dissolved in DMAc at a flow rate of 50 g/min. This solution was used as the additive solution B13.
將在實施例3所調製之高分子溶液A2、如上所述之添加劑溶液B13分別以94.9重量%及5.1重量%之比率均勻混合,以作為紡絲溶液D13。The polymer solution A2 prepared in Example 3 and the additive solution B13 as described above were uniformly mixed at a ratio of 94.9 wt% and 5.1 wt%, respectively, to obtain a spinning solution D13.
將該紡絲溶液D13在設定導輥與捲取機之速度比為1.20、及以600公尺/分鐘之紡絲速度實施乾式紡絲並加以捲取,以製造22 dtex、2絲之複絲之聚胺基甲酸酯彈性紗(500克之紗線捲裝)。The spinning solution D13 was dry-spun and wound up at a speed ratio of 1.20 and a spinning speed of 600 m/min to produce a 22 dtex, 2 filament multifilament. Polyurethane elastomer yarn (500 g yarn package).
用於構成所製得之聚胺基甲酸酯彈性紗的各成份之組成(重量%)係如表3所示,(a)化合物、(b)化合物及(c)含氮芳香族化合物係分別含有2.0重量%、3.0重量%及0.1重量%。The composition (% by weight) of each component constituting the obtained polyurethane elastic yarn is shown in Table 3, (a) compound, (b) compound, and (c) nitrogen-containing aromatic compound system. It is contained in an amount of 2.0% by weight, 3.0% by weight, and 0.1% by weight, respectively.
從所製得之聚胺基甲酸酯彈性紗(22 dtex)與東麗工業股份有限公司製造之聚對苯二甲酸乙二醇酯長纖維(33 dtex、48絲)製造與實施例3之情形相同之兩路進線半平經編組織,針織坯布(聚酯系伸縮性布帛)。就該針織坯布,實施在染色時之耐熱性3之試驗,評估在附著不飽和脂肪酸與重金屬時之染色時之耐熱性。此外,將其針織坯布加以染色後評估其外觀品質。Manufactured from the obtained polyurethane elastic yarn (22 dtex) and polyethylene terephthalate long fiber (33 dtex, 48 filament) manufactured by Toray Industries, Ltd. and Example 3 In the same situation, the two lines are semi-finished, and the knitted fabric (polyester-based stretch fabric) is knitted. With respect to the knitted fabric, a test for heat resistance 3 at the time of dyeing was carried out, and heat resistance at the time of dyeing with unsaturated fatty acid and heavy metal was evaluated. In addition, the knitted fabric was dyed and evaluated for its appearance quality.
並且,將就所製得之聚胺基甲酸酯彈性紗在反復進行染色時之耐熱性,以在染色時之耐熱性4之試驗加以評估。Further, the heat resistance of the obtained polyurethane elastic yarn upon repeated dyeing was evaluated by a test for heat resistance 4 at the time of dyeing.
該聚胺基甲酸酯彈性紗之斷裂伸度、斷裂強度、殘留 變形率、應力鬆弛率、及熱定型性之指標的熱軟化點,係皆與未混合(b)化合物、(c)化合物之比較例2(如後所述)相同,且在加工性或坯布特性方面,並未觀察到經混合此等之添加劑所引起之不良影響。Breaking elongation, breaking strength, residue of the polyurethane elastic yarn The thermal softening points of the indexes of the deformation rate, the stress relaxation rate, and the heat setting property are the same as those of the unmixed (b) compound and the compound (c), Comparative Example 2 (described later), and in the processability or the grey fabric. In terms of characteristics, no adverse effects caused by mixing such additives were observed.
此外,聚酯系伸縮性布帛在染色時之耐熱性,係在染色時之耐熱性3(對於不飽和脂肪酸與重金屬之耐性),連同在染色時之耐熱性4(對於反復進行染色之耐性),皆比比較例2顯現出大幅度地提高。並且,經加以染色所製得之伸縮性織物係無缺點,且具有優越的外觀品質者。In addition, the heat resistance of the polyester-based stretch fabric at the time of dyeing is heat resistance 3 at the time of dyeing (resistance to unsaturated fatty acids and heavy metals), together with heat resistance at the time of dyeing 4 (resistance to repeated dyeing) Both showed a significant improvement over Comparative Example 2. Further, the stretchable fabric obtained by dyeing is not disadvantageous and has superior appearance quality.
(a)化合物、(b)化合物及(c)含氮芳香族化合物係分別使用在實施例3使用之(a1)1,3,5-參(4-三級-丁基-3-羥基-2,6-二甲基苯甲基)-1,3,5-三氮-2,4,6(1H,3H,5H)-三酮、(a2)二乙烯基苯與對-甲酚之加成聚合物(杜邦公司製造之「Methacrol」(註冊商標)2390)、在實施例1所使用之(b1)具有TBDEA與PICM之6至8之重覆數的加成物,且與UDMH進行反應以在末端形成二甲基半卡肼之聚合物、以及(c2)2〔2’-羥基-3’,5’-雙(α,α-甲基苯甲基)苯基〕苯并三唑(汽巴嘉基股份有限公司製造之「TINUVIN」234、分子量為448),並將此等以1.0:1.0:3.0:0.1之比率混合,然後調製其之DMAc溶液(35重量%)。該溶液之調製,係使用與實施例3相同之方法,亦即,使用水平磨WILLY A.BACHOFEN公司製造之DYNO-MIL KDL,以填充85%之氧化鋯珠粒,且在50 克/分鐘之流速的條件下,使各成份均勻溶解於DMAc。將此溶液作為添加劑溶液B14。(a) a compound, (b) a compound, and (c) a nitrogen-containing aromatic compound are used in the (a1) 1,3,5-parameter (4-tris-butyl-3-hydroxy-) used in Example 3, respectively. 2,6-dimethylbenzyl)-1,3,5-triazole -2,4,6(1H,3H,5H)-trione, (a2) addition polymer of divinylbenzene and p-cresol (Methacrol (registered trademark) 2390 by DuPont), (b1) used in Example 1 (b1) having an adduct of 6 to 8 of TBDEA and PICM, and reacting with UDMH to form a polymer of dimethylhalocyanine at the terminal, and (c2)2 [2'-Hydroxy-3',5'-bis(α,α-methylbenzyl)phenyl]benzotriazole ("TINUVIN" 234, manufactured by Cibajiaji Co., Ltd., molecular weight 448) And these were mixed at a ratio of 1.0:1.0:3.0:0.1, and then a DMAc solution (35 wt%) thereof was prepared. The solution was prepared by the same method as in Example 3, that is, using DYNO-MIL KDL manufactured by WILLY A. BACHOFEN, Inc., to fill 85% of zirconia beads, and at 50 g/min. Under the conditions of the flow rate, the components were uniformly dissolved in DMAc. This solution was used as the additive solution B14.
將在實施例3所調製之高分子溶液A2、如上所述之添加劑溶液B14分別以94.9重量%及5.1重量%之比率均勻混合,以作為紡絲溶液D14。The polymer solution A2 prepared in Example 3 and the additive solution B14 as described above were uniformly mixed at a ratio of 94.9% by weight and 5.1% by weight, respectively, to obtain a spinning solution D14.
將該紡絲溶液D14在設定導輥與捲取機之速度比為1.20、及以600公尺/分鐘之紡絲速度實施乾式紡絲並加以捲取,以製造22 dtex、2絲之複絲之聚胺基甲酸酯彈性紗(500克之紗線捲裝)。The spinning solution D14 was dry-spun at a speed ratio of 1.20 and a spinning speed of 600 m/min at a spinning speed of the set guide roller and the coiler to produce a 22 dtex, 2 filament multifilament. Polyurethane elastomer yarn (500 g yarn package).
用於構成所製得之聚胺基甲酸酯彈性紗的各成份之組成(重量%)係如表3所示,(a)化合物、(b)化合物及(c)含氮芳香族化合物係分別含有2.0重量%、3.0重量%及0.1重量%。The composition (% by weight) of each component constituting the obtained polyurethane elastic yarn is shown in Table 3, (a) compound, (b) compound, and (c) nitrogen-containing aromatic compound system. It is contained in an amount of 2.0% by weight, 3.0% by weight, and 0.1% by weight, respectively.
從所製得之聚胺基甲酸酯彈性紗(22 dtex)與東麗工業股份有限公司製造之聚對苯二甲酸乙二醇酯長纖維(33 dtex、48絲)製造與實施例3之情形相同之兩路進線半平經編組織,以作為針織坯布(聚酯系伸縮性布帛)。就該針織坯布,實施在染色時之耐熱性3之試驗,評估在附著不飽和脂肪酸與重金屬時之染色時之耐熱性。此外,將其針織坯布加以染色後評估其外觀品質。Manufactured from the obtained polyurethane elastic yarn (22 dtex) and polyethylene terephthalate long fiber (33 dtex, 48 filament) manufactured by Toray Industries, Ltd. and Example 3 In the same situation, the two lines of the line are semi-finished and warp-knitted as a knitted fabric (polyester-based stretch fabric). With respect to the knitted fabric, a test for heat resistance 3 at the time of dyeing was carried out, and heat resistance at the time of dyeing with unsaturated fatty acid and heavy metal was evaluated. In addition, the knitted fabric was dyed and evaluated for its appearance quality.
並且,將就所製得之聚胺基甲酸酯彈性紗在反復進行染色時之耐熱性,以在染色時之耐熱性4之試驗加以評估。Further, the heat resistance of the obtained polyurethane elastic yarn upon repeated dyeing was evaluated by a test for heat resistance 4 at the time of dyeing.
該聚胺基甲酸酯彈性紗之斷裂伸度、斷裂強度、殘留 變形率、應力鬆弛率、及熱定型性之指標的熱軟化點,係皆與未混合(b)化合物、(c)化合物等之比較例2(如後所述)相同,且在加工性或坯布特性方面,並未觀察到經混合此等之添加劑所引起之不良影響。Breaking elongation, breaking strength, residue of the polyurethane elastic yarn The thermal softening points of the indexes of the deformation rate, the stress relaxation rate, and the heat setting property are the same as those of Comparative Example 2 (described later) in which the compound (b), the compound (c), and the like are not mixed, and are in processability or In terms of the characteristics of the fabric, no adverse effects caused by the mixing of the additives were observed.
此外,聚酯系伸縮性布帛在染色時之耐熱性,係在染色時之耐熱性3(對於不飽和脂肪酸與重金屬之耐性),連同在染色時之耐熱性4(對於反復進行染色之耐性),皆比比較例2顯現出大幅度地提高。但是,耐熱性4若與(c)含氮芳香族化合物以外之所有添加劑之種類、添加量為相同而僅為(c)之種類不同之實施例3相比較時,卻為稍差者。並且,經加以染色所製得之伸縮性織物係無缺點,且具有優越的外觀品質者。In addition, the heat resistance of the polyester-based stretch fabric at the time of dyeing is heat resistance 3 at the time of dyeing (resistance to unsaturated fatty acids and heavy metals), together with heat resistance at the time of dyeing 4 (resistance to repeated dyeing) Both showed a significant improvement over Comparative Example 2. However, the heat resistance 4 is slightly inferior to the third embodiment in which the types and addition amounts of all the additives other than the (c) nitrogen-containing aromatic compound are the same as those of the case of (c). Further, the stretchable fabric obtained by dyeing is not disadvantageous and has superior appearance quality.
(a)化合物、(b)化合物及(c)含氮芳香族化合物係分別使用在實施例3使用之(a1)1,3,5-參(4-三級-丁基-3-羥基-2,6-二甲基苯甲基)-1,3,5-三氮-2,4,6(1H,3H,5H)-三酮、(a2)二乙烯基苯與對-甲酚之加成聚合物(杜邦公司製造之「Methacrol」(註冊商標)2390)、(b1)具有TBDEA與PICM之6至8之重覆數的加成物,且與UDMH進行反應以在末端形成二甲基半卡肼之聚合物、以及(c1)2,4-二(2’,4’-二甲基苯基)-6-(2”-羥基-4”-烷氧基苯基)-1,3,5-三氮、且以能使(a1)為0.03重量%至1.0重量%、及(a2)為0.03重量%至6.0重量%,亦即以能使(a)化合物之合計為0.06重量%至7.0重量 %之方式,而以與實施例3相同的方式分別製造紡絲溶液,並分別以與實施例3相同的方式製造22 dtex、2絲之複絲之聚胺基甲酸酯彈性紗(500克之紗線捲裝)。(a) a compound, (b) a compound, and (c) a nitrogen-containing aromatic compound are used in the (a1) 1,3,5-parameter (4-tris-butyl-3-hydroxy-) used in Example 3, respectively. 2,6-dimethylbenzyl)-1,3,5-triazole -2,4,6(1H,3H,5H)-trione, (a2) addition polymer of divinylbenzene and p-cresol (Methacrol (registered trademark) 2390, manufactured by DuPont), ( B1) an adduct having a repeat number of 6 to 8 of TBDEA and PICM, and reacting with UDMH to form a polymer of dimethylhalocyanine at the end, and (c1) 2,4-di (2' , 4'-dimethylphenyl)-6-(2"-hydroxy-4"-alkoxyphenyl)-1,3,5-triazole And (a1) is from 0.03 wt% to 1.0 wt%, and (a2) is from 0.03 wt% to 6.0 wt%, that is, the total amount of the compound (a) is from 0.06 wt% to 7.0 wt%. In the same manner as in Example 3, a spinning solution was separately produced, and a 22 dtex, 2-filament multifilament polyurethane elastic yarn (500 g of yarn) was produced in the same manner as in Example 3, respectively. Package).
用於構成所製得之聚胺基甲酸酯彈性紗的各成份之組成(重量%),係如表5所示,含有:0.06重量%至7.0重量%之(a)化合物、3.0重量%之(b)化合物、及0.10重量%之(c)含氮芳香族化合物。The composition (% by weight) of each component constituting the obtained polyurethane elastic yarn was as shown in Table 5, and contained: 0.06 wt% to 7.0 wt% of (a) compound, 3.0 wt% (b) a compound, and 0.10% by weight of (c) a nitrogen-containing aromatic compound.
從分別所製得之聚胺基甲酸酯彈性紗(22 dtex)與東麗工業股份有限公司製造之聚對苯二甲酸乙二醇酯長纖維(33 dtex、48絲),以與實施例3之情形相同的方式分別製造兩路進線半平經編組織,以作為針織坯布(聚酯系伸縮性布帛)。就該針織坯布,實施在染色時之耐熱性3之試驗,評估在附著不飽和脂肪酸與重金屬時之染色時之耐熱性。此外,將其針織坯布加以染色後評估其外觀品質。Polyurethane elastomer yarn (23 dtex) manufactured by Dongli Industrial Co., Ltd. and polyethylene terephthalate long fiber (33 dtex, 48 filament) manufactured by Toray Industries Co., Ltd., respectively, and examples In the same manner as in the case of 3, a two-way half-warp warp structure was separately manufactured as a knitted fabric (polyester-based stretch fabric). With respect to the knitted fabric, a test for heat resistance 3 at the time of dyeing was carried out, and heat resistance at the time of dyeing with unsaturated fatty acid and heavy metal was evaluated. In addition, the knitted fabric was dyed and evaluated for its appearance quality.
並且,將就所製得之各聚胺基甲酸酯彈性紗在反復進行染色時之耐熱性,以在染色時之耐熱性4之試驗加以評估。Further, the heat resistance of each of the obtained polyurethane elastic yarns during repeated dyeing was evaluated by a test for heat resistance 4 at the time of dyeing.
該聚胺基甲酸酯彈性紗之斷裂伸度、斷裂強度、殘留變形率、應力鬆弛率、及熱定型性之指標的熱軟化點,係皆與未混合(b)化合物、(c)化合物之比較例2(如後所述)相同,且在加工性或坯布特性方面,並未觀察到經混合此等之添加劑所引起之不良影響。The thermal softening point of the elongation, fracture strength, residual deformation rate, stress relaxation rate, and heat setting property of the polyurethane elastic yarn is both unmixed (b) compound and (c) compound Comparative Example 2 (described later) was the same, and in terms of processability or fabric properties, no adverse effects caused by mixing such additives were observed.
此外,聚酯系伸縮性布帛在染色時之耐熱性,係在染色時之耐熱性3(對於不飽和脂肪酸與重金屬之耐性), 連同在染色時之耐熱性4(對於反復進行染色之耐性),皆顯現比比較例2、及未經混合(a)化合物之比較例5(如後所述)為提高。但是,實施例15及實施例16之耐熱性3及耐熱性4,若與除了(a)化合物含量為0.06重量%及0.12重量%以外,其他之所有之添加劑的種類、添加量為相同的實施例3相比較時,卻為稍差者。此外,經加以染色所製得之伸縮性織物,係大致具有優越的外觀品質者。但是,(a)化合物含量為少至0.06重量%之實施例15、(a)化合物含量為多達6重量%以上之實施例19及實施例20之外觀品質,若與實施例3相比較時,卻為稍差者。In addition, the heat resistance of the polyester-based stretch fabric during dyeing is the heat resistance 3 (durability to unsaturated fatty acids and heavy metals) during dyeing, Together with the heat resistance 4 at the time of dyeing (resistance to repeated dyeing), Comparative Example 5 (compared with Comparative Example 2) and the compound (a) which was not mixed was improved. However, the heat resistance 3 and the heat resistance 4 of Examples 15 and 16 are the same as the types and addition amounts of all other additives except that the content of the compound (a) is 0.06% by weight and 0.12% by weight. When comparing Example 3, it is a little worse. Further, the stretchable fabric obtained by dyeing has a superior appearance quality. However, (a) the content of the compound is as small as 0.06% by weight of Example 15, and the content of the compound of (a) is as high as 6% by weight or more of the appearance qualities of Example 19 and Example 20, when compared with Example 3. But it is a little worse.
(a)化合物、(b)化合物及(c)含氮芳香族化合物係分別使用在實施例3使用之(a1)1,3,5-參(4-三級-丁基-3-羥基-2,6-二甲基苯甲基)-1,3,5-三氮-2,4,6(1H,3H,5H)-三酮、(a2)二乙烯基苯與對-甲酚之加成聚合物(杜邦公司製造之「Methacrol」(註冊商標)2390)、(b1)具有TBDEA與PICM之6至8之重覆數的加成物,且與UDMH進行反應以在末端形成二甲基半卡肼之聚合物、以及(c1)2,4-二(2’,4’-二甲基苯基)-6-(2”-羥基-4”-烷氧基苯基)-1,3,5-三氮,且以(b)化合物能成為0.06重量%至7.0重量%之方式,而以表7所示之組成,且以與實施例3相同的方式分別製造紡絲溶液,並分別以與實施例3相同的方式製造22 dtex、2絲之複絲之聚胺基甲 酸酯彈性紗(500克之紗線捲裝)。(a) a compound, (b) a compound, and (c) a nitrogen-containing aromatic compound are used in the (a1) 1,3,5-parameter (4-tris-butyl-3-hydroxy-) used in Example 3, respectively. 2,6-dimethylbenzyl)-1,3,5-triazole -2,4,6(1H,3H,5H)-trione, (a2) addition polymer of divinylbenzene and p-cresol (Methacrol (registered trademark) 2390, manufactured by DuPont), ( B1) an adduct having a repeat number of 6 to 8 of TBDEA and PICM, and reacting with UDMH to form a polymer of dimethylhalocyanine at the end, and (c1) 2,4-di (2' , 4'-dimethylphenyl)-6-(2"-hydroxy-4"-alkoxyphenyl)-1,3,5-triazole And the composition of the compound (b) can be 0.06 wt% to 7.0 wt%, and the composition shown in Table 7 is used, and the spinning solution is separately produced in the same manner as in the example 3, and respectively and in the same manner as in the example 3 A 22 dtex, 2 filament multifilament polyurethane elastomer yarn (500 g yarn package) was produced in the same manner.
用於構成所製得之聚胺基甲酸酯彈性紗的各成份之組成(重量%)係如表7所示,含有:2.0重量%之(a)化合物、0.06重量%至7.0重量%之(b)化合物、及0.10重量%之(c)含氮芳香族化合物。The composition (% by weight) of each component constituting the obtained polyurethane elastic yarn was as shown in Table 7, and contained: 2.0% by weight of the compound (a), and 0.06% by weight to 7.0% by weight. (b) a compound, and 0.10% by weight of (c) a nitrogen-containing aromatic compound.
從分別所製得之聚胺基甲酸酯彈性紗(22 dtex)與東麗工業股份有限公司製造之聚對苯二甲酸乙二醇酯長纖維(33 dtex、48絲),以與實施例3之情形相同的方式分別製造兩路進線半平經編組織,以作為針織坯布(聚酯系伸縮性布帛)。就該針織坯布,實施在染色時之耐熱性3之試驗,評估在附著不飽和脂肪酸與重金屬時之染色時之耐熱性。此外,將其針織坯布加以染色後評估其外觀品質。Polyurethane elastomer yarn (23 dtex) manufactured by Dongli Industrial Co., Ltd. and polyethylene terephthalate long fiber (33 dtex, 48 filament) manufactured by Toray Industries Co., Ltd., respectively, and examples In the same manner as in the case of 3, a two-way half-warp warp structure was separately manufactured as a knitted fabric (polyester-based stretch fabric). With respect to the knitted fabric, a test for heat resistance 3 at the time of dyeing was carried out, and heat resistance at the time of dyeing with unsaturated fatty acid and heavy metal was evaluated. In addition, the knitted fabric was dyed and evaluated for its appearance quality.
並且,將就所製得之各聚胺基甲酸酯彈性紗在反復進行染色時之耐熱性,以在染色時之耐熱性4之試驗加以評估。Further, the heat resistance of each of the obtained polyurethane elastic yarns during repeated dyeing was evaluated by a test for heat resistance 4 at the time of dyeing.
該聚胺基甲酸酯彈性紗之斷裂伸度、斷裂強度、殘留變形率、應力鬆弛率、及熱定型性之指標的熱軟化點,係皆與未混合(b)化合物、(c)化合物之比較例2(如後所述)相同,且在加工性或坯布特性方面,並未觀察到經混合此等之添加劑所引起之不良影響。The thermal softening point of the elongation, fracture strength, residual deformation rate, stress relaxation rate, and heat setting property of the polyurethane elastic yarn is both unmixed (b) compound and (c) compound Comparative Example 2 (described later) was the same, and in terms of processability or fabric properties, no adverse effects caused by mixing such additives were observed.
此外,聚酯系伸縮性布帛在染色時之耐熱性,係在染色時之耐熱性3(對於不飽和脂肪酸與重金屬之耐性),連同在染色時之耐熱性4(對於反復進行染色之耐性),皆顯現出比比較例2、及未混合(b)化合物之比較例6( 如後所述)提高。但是,實施例21及實施例22之耐熱性3及4,若與除之(b)化合物含量為0.06及0.12以外,其他之所有添加劑的種類、添加量為相同的實施例3相比較時,卻為稍差者。此外,經加以染色所製得之伸縮性織物係大致具有優越的外觀品質者。但是,實施例25及實施例26之外觀品質,若與除了(b)化合物含量為6.0重量%以上以外,其他之所有添加劑的種類、添加量為相同的實施例3相比較時,卻為稍差者。In addition, the heat resistance of the polyester-based stretch fabric at the time of dyeing is heat resistance 3 at the time of dyeing (resistance to unsaturated fatty acids and heavy metals), together with heat resistance at the time of dyeing 4 (resistance to repeated dyeing) , Comparative Example 6 showing Comparative Compound 2 and Unmixed (b) Compound Increase as described later). However, when the heat resistances 3 and 4 of Examples 21 and 22 are compared with Example 3 except that the content of the compound (b) is 0.06 and 0.12, and the type and amount of all other additives are the same, It is a little worse. Further, the stretchable fabric obtained by dyeing has a superior appearance quality. However, the appearance quality of Example 25 and Example 26 is slightly compared with Example 3 except that the content of the compound (b) is 6.0% by weight or more, and the type and amount of all other additives are the same. Poor.
將在實施例1所調製之高分子溶液A1、在實施例2使用之(a2)二乙烯基苯與對-甲酚之加成聚合物(杜邦公司製造之「Methacrol」(註冊商標)2390)之DMAc 35重量%溶液B3、及經在實施例5調製之其他之添加劑溶液Z1分別以96.5重量%、1.5重量%及2.0重量%之比率均勻混合,以作為紡絲溶液E1。將該紡絲溶液E1在設定導輥與捲取機之速度比為1.40、及以540公尺/分鐘之紡絲速度實施乾式紡絲並加以捲取,以製造20 dtex、單絲之聚胺基甲酸酯彈性紗(500克之紗線捲裝)。The polymer solution A1 prepared in Example 1 and the addition polymer of (a2) divinylbenzene and p-cresol used in Example 2 (Methacrol (registered trademark) 2390 manufactured by DuPont) The DMAc 35 wt% solution B3 and the other additive solution Z1 prepared in Example 5 were uniformly mixed at a ratio of 96.5% by weight, 1.5% by weight, and 2.0% by weight, respectively, to obtain a spinning solution E1. The spinning solution E1 was dry-spun and coiled at a speed ratio of 1.40 and a spinning speed of 540 m/min to produce a 20 dtex, monofilament polyamine. Carbide elastomer yarn (500 grams of yarn package).
用於構成所製得之聚胺基甲酸酯彈性紗的各成份之組成(重量%),係如表9所示,(a)化合物係含有1.5重量%。The composition (% by weight) of each component constituting the obtained polyurethane elastic yarn was as shown in Table 9, and the compound (a) contained 1.5% by weight.
測定該聚胺基甲酸酯彈性紗之斷裂伸度、斷裂強度、殘留變形率、應力鬆弛率、及熱軟化點,並展示於表10。The elongation at break, the breaking strength, the residual deformation ratio, the stress relaxation rate, and the thermal softening point of the polyurethane elastic yarn were measured and shown in Table 10.
使用所製得之聚胺基甲酸酯彈性紗,且與實施例1之 情形相同的方式製造耐綸系伸縮性布帛,以作為針織坯布。就該針織坯布,實施在染色時之耐熱性1之試驗,評估在附著不飽和脂肪酸與重金屬時之染色時之耐熱性。其結果,與實施例1至2相比較,卻為大幅度差者。The obtained polyurethane elastic yarn was used, and was the same as in Example 1. In the same manner, a nylon-based stretch fabric was produced in the same manner as a knitted fabric. In the knitted fabric, the heat resistance 1 at the time of dyeing was carried out, and the heat resistance at the time of dyeing the unsaturated fatty acid and the heavy metal was evaluated. As a result, compared with Examples 1 to 2, it was a large difference.
此外,將其針織坯布加以染色,評估外觀品質結果,起因於各種加工歴程造成之聚胺基甲酸酯紗的喪失彈性之局部性波紋竟每20m發生200處以上,以致其係無法令人滿意者。In addition, the knitted fabric was dyed to evaluate the appearance quality. The localized corrugation of the polyurethane yarn caused by various processing processes was more than 200 per 20 m, which made it unsatisfactory. By.
將在實施例3所調製之高分子溶液A2、在實施例2使用之(a2)二乙烯基苯與對-甲酚之加成聚合物(杜邦公司製造之「Methacrol」(註冊商標)2390)之DMAc 35重量%溶液B3、及在實施例5所調製之其他之添加劑溶液Z1分別以965重量%、1.5重量%及2.0重量%之比率均勻混合,以作為紡絲溶液E2。將該紡絲溶液E2在設定導輥與捲取機之速度比為1.20、及以600公尺/分鐘之紡絲速度實施乾式紡絲並加以捲取,以製造22 dtex、2絲之複絲之聚胺基甲酸酯彈性紗(500克之紗線捲裝)。Polymer solution A2 prepared in Example 3, addition polymer of (a2) divinylbenzene and p-cresol used in Example 2 (Methacrol (registered trademark) 2390 manufactured by DuPont) The DMAc 35 wt% solution B3 and the other additive solution Z1 prepared in Example 5 were uniformly mixed at a ratio of 965 wt%, 1.5 wt%, and 2.0 wt%, respectively, to obtain a spinning solution E2. The spinning solution E2 was dry-spun and coiled at a speed ratio of 1.20 and a spinning speed of 600 m/min to produce a 22 dtex, 2 filament multifilament. Polyurethane elastomer yarn (500 g yarn package).
用於構成所製得之聚胺基甲酸酯彈性紗的各成份之組成(重量%)係如表9所示,(a)化合物係含有1.5重量%。The composition (% by weight) of each component constituting the obtained polyurethane elastic yarn was as shown in Table 9, and the compound (a) contained 1.5% by weight.
測定該聚胺基甲酸酯彈性紗之斷裂伸度、斷裂強度、殘留變形率、應力鬆弛率、及熱軟化點,並展示於表10。The elongation at break, the breaking strength, the residual deformation ratio, the stress relaxation rate, and the thermal softening point of the polyurethane elastic yarn were measured and shown in Table 10.
使用所製得之聚胺基甲酸酯彈性紗,並以與實施例3 之情形相同的方式,製造聚酯系伸縮性布帛,以作為針織坯布。就該針織坯布,實施在染色時之耐熱性3之試驗,評估在附著不飽和脂肪酸與重金屬時之染色時之耐熱性。其結果,與實施例3至4相比較,卻為大幅度差者。The obtained polyurethane elastic yarn was used, and in the same manner as in Example 3 In the same manner, a polyester-based stretch fabric was produced as a knitted fabric. With respect to the knitted fabric, a test for heat resistance 3 at the time of dyeing was carried out, and heat resistance at the time of dyeing with unsaturated fatty acid and heavy metal was evaluated. As a result, compared with Examples 3 to 4, it was a large difference.
此外,將其針織坯布加以染色,評估外觀品質結果,起因於各種加工歴程造成之聚胺基甲酸酯紗的喪失彈性之局部性波紋竟每20公尺發生66處,以致其係無法令人滿意者。In addition, the knitted fabric was dyed to evaluate the appearance quality result, and the localized corrugation of the polyurethane yarn caused by various processing processes occurred 66 times per 20 meters, so that it could not be Satisfied.
(a)位阻型酚系化合物、及(c)含氮芳香族化合物係分別使用在實施例2使用之(a2)二乙烯基苯與對-甲酚之加成聚合物(杜邦公司製造之「Methacrol」(註冊商標)2390)、(a5)N,N-雙〔3-(3,5-二-三級-丁基-4-羥基苯基)丙醯基〕肼(汽巴嘉基股份有限公司製造之「IRGANOX」MD1024)、(c2)2〔2’-羥基-3’,5’-雙(α,α-甲基苯甲基)苯基〕苯并三唑(汽巴嘉基股份有限公司製造之「TINUVIN」234),並將此等以1.0:1.0:0.7之比率混合,然後調製其之DMAc溶液(35重量%)。該溶液之調製係以與實施例1相同的方法實施。將該溶液作為添加劑溶液F1。(a) a sterically hindered phenol-based compound, and (c) a nitrogen-containing aromatic compound are each used in the addition polymer of (a2) divinylbenzene and p-cresol used in Example 2 (manufactured by DuPont). "Methacrol" (registered trademark) 2390), (a5) N,N-bis[3-(3,5-di-tris-butyl-4-hydroxyphenyl)propanyl]anthrace (Cibajiaji) "IRGANOX" MD1024), (c2)2[2'-hydroxy-3',5'-bis(α,α-methylbenzyl)phenyl]benzotriazole (Cibajia) manufactured by the company "TINUVIN" 234) manufactured by Kyrgyzstan Co., Ltd., and these were mixed at a ratio of 1.0:1.0:0.7, and then a DMAc solution (35 wt%) thereof was prepared. The preparation of this solution was carried out in the same manner as in Example 1. This solution was used as the additive solution F1.
將在實施例3所調製之高分子溶液A2、如上所述之添加劑溶液F1、及經在實施例5所調製之其他之添加劑溶液C1分別以95.3重量%、2.7重量%及2.0重量%之比率均勻混合,以作為紡絲溶液E3。The polymer solution A2 prepared in Example 3, the additive solution F1 as described above, and the other additive solution C1 prepared in Example 5 were respectively at a ratio of 95.3 wt%, 2.7 wt%, and 2.0 wt%. It was uniformly mixed to serve as a spinning solution E3.
將該紡絲溶液E3在設定導輥與捲取機之速度比為1.30、及以600公尺/分鐘之紡絲速度實施乾式紡絲並加以捲取,以製造22 dtex、2絲之複絲之聚胺基甲酸酯彈性紗(500克之紗線捲裝)。The spinning solution E3 was dry-spun and coiled at a speed ratio of 1.30 and a spinning speed of 600 m/min to produce a 22 dtex, 2 filament multifilament. Polyurethane elastomer yarn (500 g yarn package).
用於構成所製得之聚胺基甲酸酯彈性紗的各成份之組成(重量%)係如表9所示,(a)化合物、(b)化合物及(c)含氮芳香族化合物係分別含有2.0重量%、0.0重量%及0.7重量%。該聚胺基甲酸酯彈性紗係含有比較多的苯并三唑系紫外線吸收劑者。The composition (% by weight) of each component constituting the obtained polyurethane elastic yarn is as shown in Table 9, (a) compound, (b) compound, and (c) nitrogen-containing aromatic compound system. It is contained in an amount of 2.0% by weight, 0.0% by weight, and 0.7% by weight, respectively. The polyurethane elastic yarn contains a relatively large amount of a benzotriazole-based ultraviolet absorber.
該聚胺基甲酸酯彈性紗之斷裂伸度、斷裂強度、殘留變形率、應力鬆弛率、及熱軟化點,係如表10所示。The elongation at break, the breaking strength, the residual deformation ratio, the stress relaxation rate, and the thermal softening point of the polyurethane elastic yarn are shown in Table 10.
使用所製得之聚胺基甲酸酯彈性紗,並以與實施例3之情形相同的方式,製造聚酯系伸縮性布帛,以作為針織坯布。就該針織坯布,實施在染色時之耐熱性3之試驗,評估在附著不飽和脂肪酸與重金屬時之染色時之耐熱性。其結果,與實施例3至6相比較,卻為大幅度差者。Using the obtained polyurethane elastic yarn, a polyester-based stretch fabric was produced in the same manner as in the case of Example 3 as a knitted fabric. With respect to the knitted fabric, a test for heat resistance 3 at the time of dyeing was carried out, and heat resistance at the time of dyeing with unsaturated fatty acid and heavy metal was evaluated. As a result, compared with Examples 3 to 6, it was a large difference.
此外,將其針織坯布加以染色,評估外觀品質結果,起因於各種加工歴程造成之聚胺基甲酸酯紗的喪失彈性之局部性波紋竟每20公尺發生40處,以致其係無法令人滿意者。In addition, the knitted fabric was dyed to evaluate the appearance quality result, and the localized corrugation of the polyurethane yarn caused by various processing processes occurred at 40 places every 20 meters, so that it could not be Satisfied.
(a)化合物、(b)化合物及(c)含氮芳香族化合物係分別使用在實施例1所使用之(a1)1,3,5-參(4-三級-丁基-3-羥基-2,6-二甲基苯甲基)-1,3,5-三氮-2,4,6( 1H,3H,5H)-三酮、在實施例2使用之(a2)二乙烯基苯與對-甲酚之加成聚合物(杜邦公司製造之「Methacrol」(註冊商標)2390)、在實施例1所使用之(b1)具有TBDEA與PICM之6至8之重覆數的加成物,且與UDMH進行反應以在末端形成二甲基半卡肼之聚合物、以及在實施例1所使用之(c1)2,4-二(2’,4’-二甲基苯基)-6-(2”-羥基-4”-烷氧基苯基)-1,3,5-三氮,並將此等以1.0:1.0:3.0:0.8之比率混合,然後調製其之DMAc溶液(35重量%)。該溶液之調製係以與實施例1相同的方式法實施。將該溶液作為添加劑溶液F2。(a) Compound, (b) Compound, and (c) Nitrogen-Containing Aromatic Compound (a1) 1,3,5-parade (4-tris-butyl-3-hydroxyl group used in Example 1) -2,6-dimethylbenzyl)-1,3,5-triazole -2,4,6( 1H,3H,5H)-trione, (a2) addition polymer of divinylbenzene and p-cresol used in Example 2 (Methacrol, manufactured by DuPont) (trademark) 2390), (b1) an adduct having a repeat number of 6 to 8 of TBDEA and PICM used in Example 1, and reacting with UDMH to form a polymer of dimethylhaloquinone at the end And (c1) 2,4-bis(2',4'-dimethylphenyl)-6-(2"-hydroxy-4"-alkoxyphenyl)-1 used in Example 1. , 3,5-trinitrogen And these were mixed at a ratio of 1.0:1.0:3.0:0.8, and then a DMAc solution (35 wt%) thereof was prepared. The preparation of this solution was carried out in the same manner as in Example 1. This solution was used as the additive solution F2.
將在實施例3所調製之高分子溶液A2、如上所述之添加劑溶液F2分別以94.2重量%及5.8重量%之比率均勻混合,以作為紡絲溶液E4。The polymer solution A2 prepared in Example 3 and the additive solution F2 as described above were uniformly mixed at a ratio of 94.2% by weight and 5.8% by weight, respectively, to obtain a spinning solution E4.
將該紡絲溶液E4在設定導輥與捲取機之速度比為1.30、及以600公尺/分鐘之紡絲速度實施乾式紡絲並加以捲取,以製造22 dtex、2絲之複絲之聚胺基甲酸酯彈性紗(500克之紗線捲裝)。The spinning solution E4 was dry-spun and wound up at a speed ratio of 1.30 and a spinning speed of 600 m/min to produce a 22 dtex, 2 filament multifilament. Polyurethane elastomer yarn (500 g yarn package).
用於構成所製得之聚胺基甲酸酯彈性紗的各成份之組成(重量%)係如表9所示,(a)化合物、(b)化合物及(c)含氮芳香族化合物係分別含有2.0重量%、3.0重量%及0.8重量%。該聚胺基甲酸酯彈性紗係含有比較多的三氮系紫外線吸收劑者。The composition (% by weight) of each component constituting the obtained polyurethane elastic yarn is as shown in Table 9, (a) compound, (b) compound, and (c) nitrogen-containing aromatic compound system. It is contained in an amount of 2.0% by weight, 3.0% by weight, and 0.8% by weight, respectively. The polyurethane elastic yarn system contains more trinitrogen It is a UV absorber.
該聚胺基甲酸酯彈性紗之斷裂伸度、斷裂強度、殘留變形率、應力鬆弛率、及熱軟化點展示於表10。The elongation at break, breaking strength, residual deformation ratio, stress relaxation rate, and thermal softening point of the polyurethane elastic yarn are shown in Table 10.
使用所製得之聚胺基甲酸酯彈性紗,並以與實施例3之情形相同的方式,製造聚酯系伸縮性布帛,以作為針織坯布。就該針織坯布,實施在染色時之耐熱性3之試驗,評估在附著不飽和脂肪酸與重金屬時之染色時之耐熱性。其結果,與實施例3至6相比較,卻為大幅度差者。Using the obtained polyurethane elastic yarn, a polyester-based stretch fabric was produced in the same manner as in the case of Example 3 as a knitted fabric. With respect to the knitted fabric, a test for heat resistance 3 at the time of dyeing was carried out, and heat resistance at the time of dyeing with unsaturated fatty acid and heavy metal was evaluated. As a result, compared with Examples 3 to 6, it was a large difference.
此外,將其針織坯布加以染色,評估外觀品質結果,起因於各種加工歴程造成之聚胺基甲酸酯紗的喪失彈性之局部性波紋竟每20公尺發生100處以上,以致其係無法令人滿意者。In addition, the knitted fabric was dyed to evaluate the appearance quality result, and the localized corrugation of the polyurethane yarn caused by various processing processes was more than 100 per 20 meters, so that it could not be People are satisfied.
(a)化合物則未混合、(b)化合物及(c)含氮芳香族化合物係分別使用在實施例3使用之(b1)具有TBDEA與PICM之6至8之重覆數的加成物,且與UDMH進行反應以在末端形成二甲基半卡肼之聚合物、以及(c1)2,4-二(2’,4’-二甲基苯基)-6-(2”-羥基-4”-烷氧基苯基)-1,3,5-三氮,並以表9所示之組成,亦即(a)化合物則未混合而在0重量%下,以與實施例3相同之手法分別製造紡絲溶液,並分別以與實施例3相同的方式製造22 dtex、2絲之複絲之聚胺基甲酸酯彈性紗(500克之紗線捲裝)。(a) the compound is not mixed, the (b) compound and (c) the nitrogen-containing aromatic compound are each used in the embodiment (b1) having an overlap of 6 to 8 of TBDEA and PICM. And reacting with UDMH to form a polymer of dimethylhalocyanine at the end, and (c1) 2,4-bis(2',4'-dimethylphenyl)-6-(2"-hydroxy- 4"-alkoxyphenyl)-1,3,5-triazole And the composition shown in Table 9, that is, the compound (a) was not mixed, and at 0% by weight, the spinning solution was separately produced in the same manner as in Example 3, and in the same manner as in Example 3, respectively. A 22 dtex, 2 filament multifilament polyurethane yarn (500 g yarn package) was produced.
用於構成所製得之聚胺基甲酸酯彈性紗的各成份之組成(重量%)係如表9所示,並測定該聚胺基甲酸酯彈性紗之斷裂伸度、斷裂強度、殘留變形率、應力鬆弛率、及熱軟化點而展示於表10。The composition (% by weight) of each component constituting the obtained polyurethane elastic yarn was as shown in Table 9, and the elongation at break, the breaking strength, and the breaking strength of the polyurethane elastic yarn were measured. The residual deformation rate, the stress relaxation rate, and the thermal softening point are shown in Table 10.
使用所製得之聚胺基甲酸酯彈性紗,並以與實施例3之情形相同的方式,製造聚酯系伸縮性布帛,以作為針織坯布。就該針織坯布,實施在染色時之耐熱性3之試驗,評估在附著不飽和脂肪酸與重金屬時之染色時之耐熱性。其結果,與實施例15至20相比較,卻為大幅度差者。至於耐熱性4方面,也在反復進行熱處理中發生斷紗,以致為大幅度差者。Using the obtained polyurethane elastic yarn, a polyester-based stretch fabric was produced in the same manner as in the case of Example 3 as a knitted fabric. With respect to the knitted fabric, a test for heat resistance 3 at the time of dyeing was carried out, and heat resistance at the time of dyeing with unsaturated fatty acid and heavy metal was evaluated. As a result, compared with Examples 15 to 20, it was a large difference. As for the heat resistance 4, yarn breakage occurs during repeated heat treatment, so that it is greatly deteriorated.
此外,將其針織坯布加以染色,評估外觀品質結果,起因於各種加工歴程造成之聚胺基甲酸酯紗的喪失彈性之波紋或條紋狀缺點竟每20公尺發生100處以上,以致其係無法令人滿意者。In addition, the knitted fabric was dyed to evaluate the appearance quality result, and the corrugated or striped defects of the polyurethane yarn caused by various processing processes occurred more than 100 per 20 meters, so that the system was Unsatisfactory.
(a)化合物、(b)化合物未混合、及(c)含氮芳香族化合物係分別使用在實施例3使用之(a1)1,3,5-參(4-三級-丁基-3-羥基-2,6-二甲基苯甲基)-1,3,5-三氮-2,4,6(1H,3H,5H)-三酮、(a2)二乙烯基苯與對-甲酚之加成聚合物(杜邦公司製造之「Methacrol」(註冊商標)2390)、以及(c1)2,4-二(2’,4’-二甲基苯基)-6-(2”-羥基-4”-烷氧基苯基)-1,3,5-三氮,並以表9所示之組成,且以與實施例3相同的方式分別製造紡絲溶液,並分別以與實施例3相同的方式製造22 dtex、2絲之複絲之聚胺基甲酸酯彈性紗(500克之紗線捲裝)。(a) the compound, the compound (b) is not mixed, and (c) the nitrogen-containing aromatic compound is used in the (a1) 1,3,5-parade (4-tris-butyl-3) used in Example 3, respectively. -hydroxy-2,6-dimethylbenzyl)-1,3,5-triazole -2,4,6(1H,3H,5H)-trione, (a2) addition polymer of divinylbenzene and p-cresol ("Methacrol" (registered trademark) 2390) manufactured by DuPont, and (c1) 2,4-bis(2',4'-dimethylphenyl)-6-(2"-hydroxy-4"-alkoxyphenyl)-1,3,5-triazole And the composition shown in Table 9 was used, and a spinning solution was separately produced in the same manner as in Example 3, and a polydoxy formic acid of 22 dtex and 2 filaments was produced in the same manner as in Example 3, respectively. Ester elastic yarn (500 g yarn package).
用於構成所製得之聚胺基甲酸酯彈性紗的各成份之組成(重量%)係如表9所示,將該聚胺基甲酸酯彈性紗之 斷裂伸度、斷裂強度、殘留變形率、應力鬆弛率、及熱軟化點加以測定,並展示於表10。The composition (% by weight) of each component constituting the obtained polyurethane elastic yarn was as shown in Table 9, and the polyurethane elastic yarn was used. The elongation at break, the breaking strength, the residual deformation ratio, the stress relaxation rate, and the thermal softening point were measured and shown in Table 10.
使用所製得之聚胺基甲酸酯彈性紗,並以與實施例3之情形相同的方式,製造聚酯系伸縮性布帛,以作為針織坯布。就該針織坯布,實施在染色時之耐熱性3之試驗,評估在附著不飽和脂肪酸與重金屬時之染色時之耐熱性。其結果,與實施例3、更進一步地與實施例21至26相比較,卻為大幅度差者。至於耐熱性4方面,也為大幅差者。Using the obtained polyurethane elastic yarn, a polyester-based stretch fabric was produced in the same manner as in the case of Example 3 as a knitted fabric. With respect to the knitted fabric, a test for heat resistance 3 at the time of dyeing was carried out, and heat resistance at the time of dyeing with unsaturated fatty acid and heavy metal was evaluated. As a result, compared with the third embodiment and the examples 21 to 26, the results were significantly worse. As for the heat resistance 4 aspect, it is also a big difference.
如上所述,在(a)化合物及(b)化合物之存在下,添加(c)含氮芳香族化合物,將對於耐熱性、特別是對於在附著不飽和脂肪酸與重金屬的狀態下之耐熱性或反復進行染色之耐熱性造成極大的影響。亦即,經在(a)化合物及(b)化合物之存在下添加(c)化合物之實施例,會顯現比較(c)化合物之添加量為0重量%的比較例1、2為極其顯著的耐熱性之提高。其中,由實施例1至6、實施例8、及實施例12至14,即得知(c)之添加量為0.07至0.18重量%係在顯現格外優異性能上是重要。此外,若繼續增加(c)之添加量時,則將顯現降低耐熱性之傾向。亦即,明顯的是在以提高耐光性等為主要目的而(c)之添加量為超過0.3的比較例3、4的情況,其耐熱性必然降低至與未添加(c)的比較例2相同等級。As described above, in the presence of the compound (a) and the compound (b), (c) a nitrogen-containing aromatic compound is added, which is heat resistance, particularly for the state in which an unsaturated fatty acid and a heavy metal are attached, or The heat resistance of repeated dyeing has a great influence. That is, in the examples in which the compound (c) was added in the presence of the compound (a) and the compound (b), it was found that the comparative examples 1 and 2 in which the amount of the compound (c) was added was 0% by weight, which was extremely remarkable. Increased heat resistance. Among them, from Examples 1 to 6, Example 8, and Examples 12 to 14, it was found that the addition amount of (c) of from 0.07 to 0.18% by weight is important in exhibiting exceptionally excellent performance. Further, if the amount of addition of (c) is continuously increased, the tendency to lower the heat resistance will be exhibited. In other words, in the case of Comparative Examples 3 and 4 in which the amount of addition of (c) is more than 0.3 for the purpose of improving light resistance and the like, the heat resistance is inevitably lowered to Comparative Example 2 in which (c) is not added. The same level.
根據本發明之聚胺基甲酸酯彈性紗,由於在高溫染色時即使有不飽和脂肪酸或重金屬附著於紗上也能發揮優越的耐熱性,同時具有高彈性回復性及高強伸度等之彈性紗之本來的優越特性,因此特別適合使用於經與如聚酯纖維或耐綸纖維之其他纖維混用後加以高溫染色之用途。According to the polyurethane elastic yarn of the present invention, even when unsaturated fatty acid or heavy metal adheres to the yarn at the time of high temperature dyeing, superior heat resistance can be exhibited, and elasticity such as high elastic recovery and high elongation can be exhibited. The inherent superiority of the yarn is therefore particularly suitable for use in high temperature dyeing after being mixed with other fibers such as polyester or nylon fibers.
例如,可使用於對於單獨使用本發明之聚胺基甲酸酯彈性紗的用途,也可使用於與各種纖維組合以獲得優越的伸縮性布帛之情形,且可藉由針織、梭織、帶子加工等來製成為伸縮性製品。For example, it can be used for the use of the polyurethane elastic yarn of the present invention alone, and can also be used in combination with various fibers to obtain a superior stretch fabric, and can be knitted, woven, and taped. It is processed into a stretchable product.
其可供使用的具體之用途,係包括短襪、長統襪、圓編針織物、翠可特經編織物(tricot)、游泳衣、滑雪褲、工作服 、煙火服、高爾夫球褲、簡易潛水服、胸罩、束腹、手袋等之各種纖維製品、緊身材料,並且,也包括紙尿布等衛生用品之防漏用緊身材料、防水資材之緊身材料、誘餌、人造花、電氣絕緣材、揩布、複印機除垢器、襯墊等。The specific uses that can be used include socks, stockings, circular knits, tricots, swimwear, ski pants, overalls. , various types of fiber products, tight-fitting materials such as fire-fighting suits, golf pants, simple diving suits, bras, corsets, handbags, etc., and also include leak-proof materials for waterproofing products such as disposable diapers, tight materials for waterproof materials, and baits. , artificial flowers, electrical insulation materials, crepe cloth, copier descaler, liners, etc.
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JP5688601B2 (en) * | 2011-06-23 | 2015-03-25 | 東レ・オペロンテックス株式会社 | Polyurethane yarn and fabric and swimsuit using the same |
CN105637000A (en) * | 2013-10-17 | 2016-06-01 | 三洋化成工业株式会社 | Polyurethane resin, polyurethane resin composition, and method for manufacturing polyurethane resin |
WO2015088062A1 (en) * | 2013-12-10 | 2015-06-18 | 주식회사 효성 | Spandex fiber having excellent chlorine resistance and discoloration resistance and method for preparing same |
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KR20100040730A (en) | 2010-04-20 |
CN101809209B (en) | 2012-08-29 |
JP5136943B2 (en) | 2013-02-06 |
CN101809209A (en) | 2010-08-18 |
HK1147295A1 (en) | 2011-08-05 |
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